新型双轴手性布朗斯特酸催化不对称傅克反应的研究
|
摘要
傅克反应是形成碳碳键的重要反应之一，而不对称傅克反应为手性芳基衍生物的合成提供了直接途径。本论文将我们小组合成得到的一系列新型的双轴手性磷酰亚胺类布朗斯特酸催化剂应用到3个不对称傅克反应中，取得了较好的催化结果。具体研究内容及结果如下：
（1）以2-萘乙酸为起始原料，经过环化、偶联、拆分，还原得到光学纯2,2’-二苯基-[3,3’-联菲]-4,4’-二醇（VAPOL），并将（R）-VAPOL衍生化得到（R）-VAPOL磷酰氯以及磷酰胺。以（R）-VAPOL及（R）-1,1’-联-2-萘酚（BINOL）衍生的磷酰氯与（R）-VAPOL衍生的磷酰胺缩合得到3个目标产物双轴手性磷酰亚胺催化剂，并测定了化合物的熔点、旋光度、核磁氢谱、核磁碳谱、核磁磷谱、红外光谱和高分辨质谱。
（2）将（R）-BINOL及（R）-VAPOL衍生的11个双轴手性磷酰亚胺催化剂应用到吲哚与芳香醛磺酰亚胺的不对称傅克反应中，依次考察了催化剂及催化剂的用量、底物用量、添加剂及添加剂用量等因素对反应活性和立体选择性的影响。在最佳催化条件下（室温下，甲苯作为溶剂，1当量的吲哚，1当量的亚胺，2mol%3,3’位为1-萘基的（R）-BINOL衍生的磷酰亚胺作为催化剂，0.2mol%4-二甲氨基吡啶（DMAP）作为添加剂），考察了催化剂对24种芳香醛亚胺和5种吲哚反应的普适性，结果：吲哚与芳香醛磺酰亚胺的不对称傅克反应产物的产率在90-99%，对映选择性在98->99%。将吲哚与邻溴苯甲醛磺酰亚胺的用量放大到克级，催化剂的用量可降低到0.5mol%，而产物的产率和对映选择性保持不变。该不对称傅克反应表现出五个特点：1）催化反应在室温下即得到最佳反应结果，操作方便；2)极少量DMAP的使用成功地抑制了双（吲哚基）甲烷副产物的生成，把吲哚的用量从通常的2-5当量减少到1当量，使反应更加符合原子经济性；3)无论醛亚胺的苯环上连有吸电子基团还是推电子基团，产物的收率及对映选择性均非常高，底物普适性很好；4）当催化剂的用量降到0.5mol%时，对于克量级底物，反应仍然可以顺利进行；5）底物为苯环邻位上带有取代基的醛亚胺时，催化产物的产率及对映选择性非常好，这是其他催化体系所不具备的。
（3）把4个双轴手性磷酰亚胺催化剂应用到吲哚与脂肪醛磺酰亚胺的不对称傅克反应中，依次考察了催化剂及催化剂用量、底物用量、添加剂及添加剂用量、温度等因素对反应活性和立体选择性的影响。在最佳催化条件下（0℃或-40℃下，甲苯作为溶剂，1当量的吲哚，4当量的亚胺，0.25mol%（R）-VAPOL衍生的磷酰亚胺作为催化剂，0.025mol%DMAP作为添加剂），考察了催化剂对5种脂肪醛亚胺和吲哚反应的普适性，结果：吲哚与脂肪醛磺酰亚胺的不对称傅克反应产物产率在88-93%，对映选择性在96->99%。将吲哚与异丁醛磺酰亚胺的用量放大到克级，产物的对映选择性保持不变，产率有所提高。该不对称傅克反应表现出三个特点：1）催化剂的用量为极少的0.25mol%；2）催化产物的对映选择性是目前为止报道当中最高的；3）DMAP的使用不但能够抑制副产物的生成，还能提高产物的对映选择性。
（4）将（R）-BINOL、（R）-VAPOL及（R）-5,5’,6,6’,7,7’,8,8’-八氢-1,1’-联-2-萘酚（H8-BINOL）衍生的12个双轴手性磷酰亚胺催化剂应用到吡咯与芳香醛磺酰亚胺的不对称傅克反应中，依次考察了催化剂及催化剂用量、溶剂及溶剂用量、温度、添加剂及添加剂用量等因素对反应活性和立体选择性的影响。在最佳催化条件下（-60℃下，0.3M甲苯作为溶剂，1.1当量的吡咯，1当量的亚胺，0.3mol%3,3’位为3,5-二（三氟甲基苯基）的（R）-H8-BINOL衍生的磷酰亚胺作为催化剂，5mg5分子筛作为添加剂），考察了催化剂对26种芳香醛亚胺和吡咯反应的普适性，结果：吡咯与芳香醛磺酰亚胺的不对称傅克反应产物的产率在40-99%，对映选择性在93->99%。其中，5分子筛的加入有效地缩短了反应时间。
（5）将（R）-BINOL、（R）-VAPOL及（R）-H8-BINOL衍生的7个双轴手性磷酰亚胺催化剂应用到吡咯与芳基乙烯基乙酰胺的不对称傅克反应中，依次考察了催化剂及催化剂用量、溶剂、添加剂及添加剂用量等因素对反应活性和立体选择性的影响。在最佳催化条件下（室温下，0.1M1,4-二氧六环作为溶剂，1.1当量的吡咯，1当量的烯胺，2mol%3,3’位为2-萘基的（R）-H8-BINOL衍生的磷酰亚胺作为催化剂，90mg5分子筛作为添加剂），考察了催化剂对18种芳基乙烯基乙酰胺和吡咯反应的普适性，结果：吡咯与芳基乙烯基乙酰胺的不对称傅克反应产物的产率在83-96%，对映选择性在72-98%。其中，5分子筛的加入能够有效抑制副产物的生成。
总之，将我们小组合成的15个双轴手性磷酰亚胺催化剂应用到3种不对称傅克反应中，考察了77个不对称傅克反应实例，得到了较好的催化结果。通过对催化剂局部结构的调整和条件的优化，使催化剂可以适用于不同的反应，希望为不对称有机催化提供一些新的思路。
Friedel-Crafts reaction is one of the most important carbon-carbon bond-formingreactions, and asymmetric Friedel-Crafts reaction is a direct way to synthesize chiralaryl derivatives. In this thesis, we synthesized a series of new double axially chiralbisphosphorylimide Br nsted acid catalyst, applied them to three types of asymmetricFriedel-Crafts reaction, and achieved good catalytic results.
The optically pure2,2’-diphenyl-[3,3’-biphenanthrene]-4,4’-diol (VAPOL) wassynthesized via a cyclization, coupling, chiral resolution and reduction sequence from2-Naphthaleneacetic acid. Further synthesis to obtain (R)-VAPOL derived phosphorylchloride and phosphoric amide.(R)-VAPOL phosphoryl chloride and (R)-1,1’-bi-2-naphthol(BINOL) phosphoryl chloride reacted with (R)-VAPOLphosphoryl amide to get the double axially chiral bisphosphorylimide Br nsted acidcatalysts. The melting point, optical rotation,1H NMR,13C NMR,31P NMR, IR,HRMS of catalysts were all characterized.
The eleven double axially chiral bisphosphorylimide catalysts derived from (R)-VAPOL and (R)-BINOL were applied to catalytic asymmetric Friedel-Crafts reactionof indoles and aryl N-tosyl imines. The effect of several factors, such as the activityand dosages of catalysts, the amount of substrate, the influence and dosages ofadditives, on reactivities and stereoselectivities of this reaction were investigated.Under the optimal conditions (Room temperature, toluene as reaction medium,1eq. indole,1eq. imine,2mol%bisphosphorylimide derived from (R)-BINOL which3,3’-position is1-naphthyl as catalyst,0.2mol%4-dimethylamiopryidine(DMAP) asadditive),24kinds of aryl imines,5kinds of indoles were also investigated. Resultly,the products of asymmetric Friedel-Crafts reaction from aryl N-tosyl imines withindoles were obtained in high enantioselectivities (98->99%ee) with high yields(90-99%). Experiments were performed on gram scales between indole and2-bromobenzaldehyde imine, at which the catalyst loading could be further reduced to0.5mol%and the product was obtained without any loss of enantioselectivity andyield. In addition, five characteristics of this Friedel-Crafts should be underlined:1)the catalytic reaction can be carried out at room temperature and easy to operate;2)The use of a very small amount of DMAP in successfully inhibited the formation ofbis (indolyl) methane byproducts, the amount of indole was reduced from common2-5equivalents to1equivalent;3) A wide range of aryl imines bearing eitherelectron-withdrawing or electron-donating groups on the phenyl ring furnished theresulting chiral3-indolymethanamines with high yields and excellentenatioselectivities in all cases;4) When the amount of the catalyst is reduced to0.5mol%, for the gram-scale reaction, the reaction can still be carried out smoothly;5)Our catalytic system was capable of promoting the Friedel–Crafts reaction ofortho-substituted aldimines with high efficiency and selectivity, whereas systems inprevious reports showed considerable chemoselective or stereoselective limitations.
Then, the four double axially chiral bisphosphorylimide catalysts derived from (R)-VAPOL and (R)-BINOL were applied to catalytic asymmetric Friedel-Crafts reactionof indoles and alkyl N-tosyl imines. The effect of several factors, such as the activityand dosages of catalysts, the amount of substrate, the influence and dosages ofadditives, the reaction temperature, on reactivities and stereoselectivities of thisreaction were investigated. Under the optimal catalytic conditions (0℃or-40℃,toluene as reaction medium,1eq. indole,4eq. imine,0.25mol%bisphosphorylimidederived from (R)-VAPOL as catalyst,0.025mol%DMAP as additive),5kinds ofalkyl imines were also investigated. Resultly, the products of asymmetric Friedel-Crafts reaction from alkyl N-tosyl imines with indoles were obtained in highenantioselectivities (96->99%ee) with high yields (88-93%). Experiments wereperformed on gram scales between indole and isobutyraldehyde imine, at which theenantioselectivity of the product remain unchanged, and the yield was improved. Inaddition, three characteristics of this Friedel-Crafts should be underlined:1) Theamount of catalyst is0.25mol%, is very small;2) Enantioselectivity of the catalyticproduct is the highest in so far reports;3) DMAP in use not only suppress theformation of byproducts, but also improve the enantioselectivity of the product.
In addition, the twelve double axially chiral bisphosphorylimide catalysts derivedfrom (R)-5,5’,6,6’,7,7’,8,8’-octahydro-1,1-bi-2-naphtol(H8-BINOL),(R)-BINOL and(R)-VAPOL were applied to catalytic asymmetric Friedel-Crafts reaction of pyrrolesand aryl N-tosyl imines. The effect of several factors, such as the activity and dosagesof catalysts, the solvents, the influence and dosages of additives and the reactiontemperature, on reactivities and stereoselectivities of this reaction were investigated.Under the optimal catalytic conditions (-60℃, toluene(0.3M) as reaction medium,1.1eq. pyrrole,1eq. imine,0.3mol%bisphosphorylimide derived from(R)-H8-BINOL which3,3’-position is3,5-bis (trifluoromethyl) phenyl as catalyst,5mg5molecular sieve as additive),23kinds of aryl imines were also investigated.Resultly, the products of asymmetric Friedel-Crafts reaction from aryl N-tosyl imineswith pyrrole were obtained in high enantioselectivities (93->99%ee) with moderateyields (40-99%).5molecular sieve added to shorten the reaction time.
Finally, the seven double axially chiral bisphosphorylimide catalysts derived from(R)-BINOL,(R)-VAPOL and (R)-H8-BINOL were applied to catalytic asymmetricFriedel-Crafts reaction of pyrroles and α-aryl enamides. The effect of several factors,such as the activity and dosages of catalysts, the solvents, the influence and dosagesof additives, on reactivities and stereoselectivities of this reaction were investigated.Under the optimal catalytic conditions(Room temperature, dioxane as reactionmedium,1.1eq. pyrrole,1eq. enamide,2mol%bisphosphorylimide derived from (R)-H8-BINOL which3,3’-position is2-naphthyl as catalyst,90mg5molecularsieve as additive),18kinds of α-aryl enamides were also investigated. Resultly, theproducts of asymmetric Friedel-Crafts reaction from aryl N-tosyl imines with pyrrolewere obtained in high enantioselectivities (72-98%ee) with high yields (83-96%).5molecular sieve added to effectively suppressed the formation of byproducts.
Overall, the fifteen double axially chiral bisphosphorylimide catalysts wereapplied to catalytic three types of asymmetric Friedel-Crafts reaction.77catalyticasymmetric Friedel-Crafts reaction instances were investigated. Via the researchingwork of this dissertation, it can provide experimental data for the application of thedouble axially chiral bisphosphorylimide catalysts. Moreover, some of the additives incatalytic reactions attempts play a unique role, and we hope that it can provide somenew ideas for asymmetric organic synthesis.
（1）以2-萘乙酸为起始原料，经过环化、偶联、拆分，还原得到光学纯2,2’-二苯基-[3,3’-联菲]-4,4’-二醇（VAPOL），并将（R）-VAPOL衍生化得到（R）-VAPOL磷酰氯以及磷酰胺。以（R）-VAPOL及（R）-1,1’-联-2-萘酚（BINOL）衍生的磷酰氯与（R）-VAPOL衍生的磷酰胺缩合得到3个目标产物双轴手性磷酰亚胺催化剂，并测定了化合物的熔点、旋光度、核磁氢谱、核磁碳谱、核磁磷谱、红外光谱和高分辨质谱。
（2）将（R）-BINOL及（R）-VAPOL衍生的11个双轴手性磷酰亚胺催化剂应用到吲哚与芳香醛磺酰亚胺的不对称傅克反应中，依次考察了催化剂及催化剂的用量、底物用量、添加剂及添加剂用量等因素对反应活性和立体选择性的影响。在最佳催化条件下（室温下，甲苯作为溶剂，1当量的吲哚，1当量的亚胺，2mol%3,3’位为1-萘基的（R）-BINOL衍生的磷酰亚胺作为催化剂，0.2mol%4-二甲氨基吡啶（DMAP）作为添加剂），考察了催化剂对24种芳香醛亚胺和5种吲哚反应的普适性，结果：吲哚与芳香醛磺酰亚胺的不对称傅克反应产物的产率在90-99%，对映选择性在98->99%。将吲哚与邻溴苯甲醛磺酰亚胺的用量放大到克级，催化剂的用量可降低到0.5mol%，而产物的产率和对映选择性保持不变。该不对称傅克反应表现出五个特点：1）催化反应在室温下即得到最佳反应结果，操作方便；2)极少量DMAP的使用成功地抑制了双（吲哚基）甲烷副产物的生成，把吲哚的用量从通常的2-5当量减少到1当量，使反应更加符合原子经济性；3)无论醛亚胺的苯环上连有吸电子基团还是推电子基团，产物的收率及对映选择性均非常高，底物普适性很好；4）当催化剂的用量降到0.5mol%时，对于克量级底物，反应仍然可以顺利进行；5）底物为苯环邻位上带有取代基的醛亚胺时，催化产物的产率及对映选择性非常好，这是其他催化体系所不具备的。
（3）把4个双轴手性磷酰亚胺催化剂应用到吲哚与脂肪醛磺酰亚胺的不对称傅克反应中，依次考察了催化剂及催化剂用量、底物用量、添加剂及添加剂用量、温度等因素对反应活性和立体选择性的影响。在最佳催化条件下（0℃或-40℃下，甲苯作为溶剂，1当量的吲哚，4当量的亚胺，0.25mol%（R）-VAPOL衍生的磷酰亚胺作为催化剂，0.025mol%DMAP作为添加剂），考察了催化剂对5种脂肪醛亚胺和吲哚反应的普适性，结果：吲哚与脂肪醛磺酰亚胺的不对称傅克反应产物产率在88-93%，对映选择性在96->99%。将吲哚与异丁醛磺酰亚胺的用量放大到克级，产物的对映选择性保持不变，产率有所提高。该不对称傅克反应表现出三个特点：1）催化剂的用量为极少的0.25mol%；2）催化产物的对映选择性是目前为止报道当中最高的；3）DMAP的使用不但能够抑制副产物的生成，还能提高产物的对映选择性。
（4）将（R）-BINOL、（R）-VAPOL及（R）-5,5’,6,6’,7,7’,8,8’-八氢-1,1’-联-2-萘酚（H8-BINOL）衍生的12个双轴手性磷酰亚胺催化剂应用到吡咯与芳香醛磺酰亚胺的不对称傅克反应中，依次考察了催化剂及催化剂用量、溶剂及溶剂用量、温度、添加剂及添加剂用量等因素对反应活性和立体选择性的影响。在最佳催化条件下（-60℃下，0.3M甲苯作为溶剂，1.1当量的吡咯，1当量的亚胺，0.3mol%3,3’位为3,5-二（三氟甲基苯基）的（R）-H8-BINOL衍生的磷酰亚胺作为催化剂，5mg5分子筛作为添加剂），考察了催化剂对26种芳香醛亚胺和吡咯反应的普适性，结果：吡咯与芳香醛磺酰亚胺的不对称傅克反应产物的产率在40-99%，对映选择性在93->99%。其中，5分子筛的加入有效地缩短了反应时间。
（5）将（R）-BINOL、（R）-VAPOL及（R）-H8-BINOL衍生的7个双轴手性磷酰亚胺催化剂应用到吡咯与芳基乙烯基乙酰胺的不对称傅克反应中，依次考察了催化剂及催化剂用量、溶剂、添加剂及添加剂用量等因素对反应活性和立体选择性的影响。在最佳催化条件下（室温下，0.1M1,4-二氧六环作为溶剂，1.1当量的吡咯，1当量的烯胺，2mol%3,3’位为2-萘基的（R）-H8-BINOL衍生的磷酰亚胺作为催化剂，90mg5分子筛作为添加剂），考察了催化剂对18种芳基乙烯基乙酰胺和吡咯反应的普适性，结果：吡咯与芳基乙烯基乙酰胺的不对称傅克反应产物的产率在83-96%，对映选择性在72-98%。其中，5分子筛的加入能够有效抑制副产物的生成。
总之，将我们小组合成的15个双轴手性磷酰亚胺催化剂应用到3种不对称傅克反应中，考察了77个不对称傅克反应实例，得到了较好的催化结果。通过对催化剂局部结构的调整和条件的优化，使催化剂可以适用于不同的反应，希望为不对称有机催化提供一些新的思路。
Friedel-Crafts reaction is one of the most important carbon-carbon bond-formingreactions, and asymmetric Friedel-Crafts reaction is a direct way to synthesize chiralaryl derivatives. In this thesis, we synthesized a series of new double axially chiralbisphosphorylimide Br nsted acid catalyst, applied them to three types of asymmetricFriedel-Crafts reaction, and achieved good catalytic results.
The optically pure2,2’-diphenyl-[3,3’-biphenanthrene]-4,4’-diol (VAPOL) wassynthesized via a cyclization, coupling, chiral resolution and reduction sequence from2-Naphthaleneacetic acid. Further synthesis to obtain (R)-VAPOL derived phosphorylchloride and phosphoric amide.(R)-VAPOL phosphoryl chloride and (R)-1,1’-bi-2-naphthol(BINOL) phosphoryl chloride reacted with (R)-VAPOLphosphoryl amide to get the double axially chiral bisphosphorylimide Br nsted acidcatalysts. The melting point, optical rotation,1H NMR,13C NMR,31P NMR, IR,HRMS of catalysts were all characterized.
The eleven double axially chiral bisphosphorylimide catalysts derived from (R)-VAPOL and (R)-BINOL were applied to catalytic asymmetric Friedel-Crafts reactionof indoles and aryl N-tosyl imines. The effect of several factors, such as the activityand dosages of catalysts, the amount of substrate, the influence and dosages ofadditives, on reactivities and stereoselectivities of this reaction were investigated.Under the optimal conditions (Room temperature, toluene as reaction medium,1eq. indole,1eq. imine,2mol%bisphosphorylimide derived from (R)-BINOL which3,3’-position is1-naphthyl as catalyst,0.2mol%4-dimethylamiopryidine(DMAP) asadditive),24kinds of aryl imines,5kinds of indoles were also investigated. Resultly,the products of asymmetric Friedel-Crafts reaction from aryl N-tosyl imines withindoles were obtained in high enantioselectivities (98->99%ee) with high yields(90-99%). Experiments were performed on gram scales between indole and2-bromobenzaldehyde imine, at which the catalyst loading could be further reduced to0.5mol%and the product was obtained without any loss of enantioselectivity andyield. In addition, five characteristics of this Friedel-Crafts should be underlined:1)the catalytic reaction can be carried out at room temperature and easy to operate;2)The use of a very small amount of DMAP in successfully inhibited the formation ofbis (indolyl) methane byproducts, the amount of indole was reduced from common2-5equivalents to1equivalent;3) A wide range of aryl imines bearing eitherelectron-withdrawing or electron-donating groups on the phenyl ring furnished theresulting chiral3-indolymethanamines with high yields and excellentenatioselectivities in all cases;4) When the amount of the catalyst is reduced to0.5mol%, for the gram-scale reaction, the reaction can still be carried out smoothly;5)Our catalytic system was capable of promoting the Friedel–Crafts reaction ofortho-substituted aldimines with high efficiency and selectivity, whereas systems inprevious reports showed considerable chemoselective or stereoselective limitations.
Then, the four double axially chiral bisphosphorylimide catalysts derived from (R)-VAPOL and (R)-BINOL were applied to catalytic asymmetric Friedel-Crafts reactionof indoles and alkyl N-tosyl imines. The effect of several factors, such as the activityand dosages of catalysts, the amount of substrate, the influence and dosages ofadditives, the reaction temperature, on reactivities and stereoselectivities of thisreaction were investigated. Under the optimal catalytic conditions (0℃or-40℃,toluene as reaction medium,1eq. indole,4eq. imine,0.25mol%bisphosphorylimidederived from (R)-VAPOL as catalyst,0.025mol%DMAP as additive),5kinds ofalkyl imines were also investigated. Resultly, the products of asymmetric Friedel-Crafts reaction from alkyl N-tosyl imines with indoles were obtained in highenantioselectivities (96->99%ee) with high yields (88-93%). Experiments wereperformed on gram scales between indole and isobutyraldehyde imine, at which theenantioselectivity of the product remain unchanged, and the yield was improved. Inaddition, three characteristics of this Friedel-Crafts should be underlined:1) Theamount of catalyst is0.25mol%, is very small;2) Enantioselectivity of the catalyticproduct is the highest in so far reports;3) DMAP in use not only suppress theformation of byproducts, but also improve the enantioselectivity of the product.
In addition, the twelve double axially chiral bisphosphorylimide catalysts derivedfrom (R)-5,5’,6,6’,7,7’,8,8’-octahydro-1,1-bi-2-naphtol(H8-BINOL),(R)-BINOL and(R)-VAPOL were applied to catalytic asymmetric Friedel-Crafts reaction of pyrrolesand aryl N-tosyl imines. The effect of several factors, such as the activity and dosagesof catalysts, the solvents, the influence and dosages of additives and the reactiontemperature, on reactivities and stereoselectivities of this reaction were investigated.Under the optimal catalytic conditions (-60℃, toluene(0.3M) as reaction medium,1.1eq. pyrrole,1eq. imine,0.3mol%bisphosphorylimide derived from(R)-H8-BINOL which3,3’-position is3,5-bis (trifluoromethyl) phenyl as catalyst,5mg5molecular sieve as additive),23kinds of aryl imines were also investigated.Resultly, the products of asymmetric Friedel-Crafts reaction from aryl N-tosyl imineswith pyrrole were obtained in high enantioselectivities (93->99%ee) with moderateyields (40-99%).5molecular sieve added to shorten the reaction time.
Finally, the seven double axially chiral bisphosphorylimide catalysts derived from(R)-BINOL,(R)-VAPOL and (R)-H8-BINOL were applied to catalytic asymmetricFriedel-Crafts reaction of pyrroles and α-aryl enamides. The effect of several factors,such as the activity and dosages of catalysts, the solvents, the influence and dosagesof additives, on reactivities and stereoselectivities of this reaction were investigated.Under the optimal catalytic conditions(Room temperature, dioxane as reactionmedium,1.1eq. pyrrole,1eq. enamide,2mol%bisphosphorylimide derived from (R)-H8-BINOL which3,3’-position is2-naphthyl as catalyst,90mg5molecularsieve as additive),18kinds of α-aryl enamides were also investigated. Resultly, theproducts of asymmetric Friedel-Crafts reaction from aryl N-tosyl imines with pyrrolewere obtained in high enantioselectivities (72-98%ee) with high yields (83-96%).5molecular sieve added to effectively suppressed the formation of byproducts.
Overall, the fifteen double axially chiral bisphosphorylimide catalysts wereapplied to catalytic three types of asymmetric Friedel-Crafts reaction.77catalyticasymmetric Friedel-Crafts reaction instances were investigated. Via the researchingwork of this dissertation, it can provide experimental data for the application of thedouble axially chiral bisphosphorylimide catalysts. Moreover, some of the additives incatalytic reactions attempts play a unique role, and we hope that it can provide somenew ideas for asymmetric organic synthesis.
引文
[1]张殷全.Friedel-Crafts反应的发现史[J].化学通报，2000（7）：59-62.
[2] Giuseppe Bartoli, Giorgio Bencivenni, Renato Dalpozzo. Organocatalyticstrategies for the asymmetric functionalization of indoles[J].Chem. Soc. Rev.,2010,39,4449-4465.
[3] Joel F. Austin, David W. C. MacMillan. Enantioselective OrganocatalyticIndole Alkylations. Design of a New and Highly Effective Chiral Amine forIminium Catalysis[J].J. Am. Chem. Soc.,2002,124,1172-1173.
[4] Sung-Gon Kim. Organocatalytic Asymmetric Friedel-Crafts Alkylation toγ-Hydroxy α,β-Unsaturated Aldehyde[J].Bull. Korean Chem. Soc.,2009,30,2519-2520.
[5] Stephen Hanessian, Eli Stoffman, Xueling Mi, Paul Renton. Applications ofOrganocatalytic Asymmetric Synthesis to Drug Prototypes-Dual Action andSelective Inhibitors of n-Nitric Oxide Synthase with Activity Against the5-HT1D/1BSubreceptors[J].Org. Lett.,2011,13,840-843.
[6] Chang-Feng Li, Hiu Liu, Jie Liao, Yi-Ju Cao, Xiao-Peng Liu, Wen-Jing Xiao.Enantioselective Organocatalytic Intramolecular Ring-Closing Friedel-Crafts-Type Alkylation of Indoles[J].Org. Lett.,2007,9,1847-1850.
[7] Ying-Cen Guo, Dong-Ping Li, Yu-Ling Li, Hong-Mei Wang, Wen-Jing Xiao.Asymmetric Friedel-Crafts Alkylations of Indoles with Dialkyl3-Oxoprop-1-enylphosphonates: Organocatalytic Enantioselective Synthesis of α-IndolylPhosphonates[J].Chirality,2009,21,777-785.
[8] H. Dalton King, Zhaoxing Meng, Derek Denhart, Ronald Mattson, Roy Kimura,Dedong Wu, Qi Gao, John E. Macor. Enantioselective Synthesis of a HighlyPotent Selective Serotonin Reuptake Inhibitor. An Application of Imidazolidin-one Catalysis to the Alkylation of Indoles with an α,β-Disubstituted α,β-Unsaturated Aldehyde[J].Org. Lett.,2005,7,3437-3440.
[9] Mauro Marigo, Tobias C. Wabnitz, Doris Fielenbach, Karl Anker J rgensen.Enantioselective Organocatalyzed a Sulfenylation of Aldehydes[J].Angew.Chem. Int. Ed.,2005,44,794-797.
[10] Yujiro Hayashi, Hiroaki Gotoh, Takaaki Hayashi, Mitsuru Shoji.Diphenylprolinol Silyl Ethers as Efficient Organocatalysts for the AsymmetricMichael Reaction of Aldehydes and Nitroalkenes[J].Angew. Chem. Int. Ed.,2005,44,4212-4215.
[11] A. Lattanzi. α,α-Diarylprolinols: bifunctional organocatalysts for asymmetricsynthesis[J].Chem. Commun.,2009,1452–1463.
[12] A. Mielgo, C. Palomo. α,α-Diarylprolinol Ethers: New Tools forFunctionalization of Carbonyl Compounds[J].Chem.Asian J.,2008,3,922-948.
[13] Zhi-Jing Wang, Jian-Guo Yang, Jun Jin, Xin Lv, Weiliang Bao. Enantio-selective Friedel–Crafts alkylation of indoles with aromatic α,β-unsaturatedaldehydes catalyzed by diphenylprolinol silyl ether[J].Synthesis,2009,23,3994-4000.
[14] H. Liang, W. Lei, C. Chao, Z. Bangzhi and R. Wang. An Efficient Enantio-selective Method for Asymmetric Friedel–Crafts Alkylation of Indoles withα,β-Unsaturated Aldehydes[J].Adv. Synth. Catal.,2009,351,772–778.
[15] Yi-Ju Cao, Hong-Gang Cheng, Liang-Qiu Lu, Ji-Ji Zhang, Ying Cheng,Jia-Rong Chen, Wen-Jing Xiao.Organocatalytic Multiple Cascade Reactions: ANew Strategy for the Construction of Enantioenriched Tetrahydrocarbazoles[J].Adv. Synth. Catal.,2011,353,617-623.
[16] Xiao-Yu Zhu, Xiao-Lei An, Chang-Feng Li, Fu-Gen Zhang, Qiu-Lin Hua,Jia-Rong Chen, Wen-Jing Xiao. A Practical and Enantioselective Approach toTetrahydrocarbazoles by Asymmetric Organocatalysis[J].ChemCatChem,2011,3,679-683.
[17] Kazutaka Shibatomi, Akira Narayama, Yoshiyuki Abe, Seiji Iwasa. Practicalsynthesis of4,4,4-trifluorocrotonaldehyde: a versatile precursor for theenantioselective formation of trifluoromethylated stereogenic centers viaorganocatalytic1,4-additions[J].Chem. Commun.,2012,48,7380–7382.
[18] Tian Tian, Baojian Pei, Qinghua Li, Hao He, Ling-Yan Chen, Xiang Zhou,Wing-Hong Chan, Albert W. M. Lee. CaSH Organocatalysis: Ena ntioselectiveFriedel–Crafts Alkylation of Indoles with α,β-unsaturated aldehydes[J].Synlett.,2009,13,2115-2118.
[19] K. Akagawa, T. Yamashita, S. Sakamoto and K. Kudo. Friedel–Crafts-typealkylation in aqueous media using resin-supported peptide catalyst havingpolyleucine[J].Tetrahedron Lett.,2009,50,5602-5604.
[20] Thomas B. Poulsen, Karl Anker J rgensen. Catalytic Asymmetric FriedelCrafts Alkylation Reactions Copper Showed the Way[J].Chem. Rev.,2008,108,2903-2915.
[21] M. Bandini, A. Melloni, A. Umani-Ronchi. New Catalytic Approaches in theStereoselective Friedel–Crafts Alkylation Reaction[J].Angew.Chem.Int.Ed.,2004,43,550-556.
[22] M. Bandini, A. Eichholzer, A. Umani-Ronchi. An Update on CatalyticEnantioselective Alkylations of Indoles[J].Mini-Rev.Org.Chem.,2007,4,115-124.
[23] D. P. Li, Y. C. Guo, Y. Ding, W. J. Xiao. Chem. Organocatalytic C3-selectiveFriedel–Crafts alkylations of indoles with α,β-unsaturated ketones[J].Chem.Commun.,2006,799-801.
[24] W. Zhou, L.-W. Xu, L. Li, L. Yang, C.-G. Xia. Enantioselective Michael-TypeFriedel-Crafts Reactions of Indoles to Enones Catalyzed by a ChiralCamphor-Based Br nsted Acid[J].Eur. J. Org.Chem.,2006,23,5225-5227.
[25] W. Chen, W. Du, L. Yue, R. Li, Y. Wu, L. S. Ding, Y. C. Chen.Organocatalytic enantioselective indole alkylations of α,β-unsaturated ketones[J].Org. Biomol. Chem.,2007,5,816-821.
[26] G. Blay, I. Fernandez, J. R. Pedro, C. Vila. Highly EnantioselectiveFriedel Crafts Alkylations of Indoles with Simple Enones Catalyzed byZirconium(IV) BINOL Complexes[J].Org. Lett.,2007,9,2601-2604.
[27] G. Bartoli, M. Bosco, A. Carlone, F. Pesciaioli, L. Sambri, P. Melchiorre.Organocatalytic Asymmetric Friedel Crafts Alkylation of Indoles with Simpleα,β-Unsaturated Ketones[J].Org. Lett.,2007,9,1403-1405.
[28] P. Ricci, A. Carlone, G. Bartoli, M. Bosco, L. Sambri, P. Melchiorre.Organocatalytic Asymmetric Sulfa-Michael Addition to α,β-UnsaturatedKetones[J].Adv. Synth. Catal.,2008,350,49-53.
[29] F. Pesciaioli, F. De Vincentiis, P. Galzerano, G. Bencivenni,G. Bartoli, A.Mazzanti, P. Melchiorre. Organocatalytic Asymmetric Aziridination of Enones[J].Angew. Chem. Int. Ed.,2008,47,8703-8706.
[30] M. Rueping, B. J. Nachtsheim, S. A. Moreth, M. Bolte. Asymmetric Br nstedAcid Catalysis: Enantioselective Nucleophilic Substitutions and1,4-Additions[J].Angew. Chem. Int. Ed.,2008,47,593-596.
[31] Chun-Hui Xing, Yuan-Xi Liao, Jaclynn Ng, Qiao-Sheng Hu. Optically Active1,1’-Spirobiindane-7,7’-diol (SPINOL)-Based Phosphoric Acids as HighlyEnantioselective Catalysts for Asymmetric Organocatalysis[J].J. Org. Chem.,2011,76,4125–4131.
[32] H.-Y. Tang, A.-D. Lu, Z.-H. Zhou, G.-F. Zhao, L.-N. He, C.-C. Tang. ChiralPhosphoric Acid Catalyzed Asymmetric Friedel–Crafts Alkylation of Indoleswith Simple α,β-Unsaturated Aromatic Ketones[J].Eur. J. Org. Chem.,2008,1406-1410.
[33] A. Scettri, R. Villano, M. Acocella. Asymmetric Friedel-Crafts Alkylation ofIndole with Chalcones Catalyzed by Chiral Phosphoric Acids[J].Molecules,2009,14,3030-3036.
[34] Tsubasa Sakamoto, Junji Itoh, Keiji Mori, Takahiko Akiyama. Chiral Br nstedacid catalyzed asymmetric Friedel–Crafts alkylation reaction of indoles withα,β-unsaturated ketones: short access to optically active2-and3-substitutedindole derivatives[J].Org. Biomol. Chem.,2010,8,5448–5454.
[35] Q. Cai, Z.-A. Zhao, S.-L. You. Asymmetric Construction of Polycyclic Indolesthrough Olefin Cross-Metathesis/Intramolecular Friedel–Crafts Alkylationunder Sequential Catalysis[J].Angew. Chem. Int. Ed.,2009,48,7428-7431.
[36] Jun-Wei Zhang, Quan Cai, Xiao-Xin Shi, Wei Zhang, Shu-Li You.Enantioselective Synthesis of Tetrahydropyrano[3,4-b]indoles Catalyzed byChiral N-Triflyl Phosphoramide via Intramolecular Friedel–Crafts AlkylationReaction[J].Synlett,2011,9,1239–1242.
[37] Zeng-kai Pei, Yan Zheng, Jing Nie, Jun-An Ma. Chiral Br nsted acid-catalyzedregio-and enantioselective arylation of α,β-unsaturated trifluoromethyl ketones[J].Tetrahedron Letters,2010,51,4658-4661.
[38] Prabhakar Bachu, Takahiko Akiyama. Enantioselective Friedel–Craftsalkylation reaction of indoles with α,β-unsaturated acyl phosphonates catalyzedby chiral phosphoric acid[J].Chem. Commun.,2010,46,4112–4114.
[39] S. Adachi, F. Tanaka, K. Watanabe, T. Harada. Oxazaborolidinone-CatalyzedEnantioselective Friedel Crafts Alkylation of Furans and Indoles withα,β-Unsaturated Ketones[J].Org. Lett.,2009,11,5206-5209.
[40] T. Arai, N. Yokoyama. Tandem Catalytic Asymmetric Friedel–Crafts/HenryReaction: Control of Three Contiguous Acyclic Stereocenters[J].Angew. Chem.Int. Ed.,2008,47,4989-4992.
[41] Y.-X. Jia, S.-F. Zhu, Y. Yang, Q.-L. Zhou. Asymmetric Friedel CraftsAlkylations of Indoles with Nitroalkenes Catalyzed by Zn(II) BisoxazolineComplexes[J].J. Org. Chem.,2006,71,75-80.
[42] P. K. Singh, A. Bisai, V. K. Singh. Enantioselective Friedel–Crafts alkylationof indoles with nitroalkenes catalyzed by a bis(oxazoline)–Cu(II) complex[J].Tetrahedron Lett.,2007,48,1127-1129.
[43] Y. Sui, L. Liu, J.-L. Zhao, D. Wang, Y.-J. Chen. Catalytic and asymmetricFriedel–Crafts alkylation of indoles with nitroacrylates. Application to thesynthesis of tryptophan analogues[J].Tetrahedron,2007,63,5173-5183.
[44] H. Liu, S.-F. Lu, J. Xu, D.-M. Du. Asymmetric Friedel–Crafts Alkylation ofElectron-Rich N-Heterocycles with Nitroalkenes Catalyzed by Diphenylamine-Tethered Bis(oxazoline) and Bis(thiazoline) ZnIIComplexes[J].Chem.Asian J.,2008,3,1111-1121.
[45] Seán C. McKeon, Helge Müller-Bunz, Patrick J. Guiry. New Thiazoline–Oxazoline Ligands and Their Application in the Asymmetric Friedel–CraftsReaction[J].Eur. J. Org. Chem.,2009,4833-4841.
[46] M. Bandini, A. Garelli, M. Rovinetti, S. Tommasi, A. Umani-Ronchi. Catalyticenantioselective addition of indoles to arylnitroalkenes: An effective route toenantiomerically enriched tryptamine precursors[J].Chirality,2005,17,522-529.
[47] Z.-L. Yuan, Z.-Y. Lei, M. Shi. BINAM and H8-BINAM-based chiral iminesand Zn(OTf)2-catalyzed enantioselective Friedel–Crafts alkylation of indoleswith nitroalkenes[J].Tetrahedron:Asymmetry,2008,19,1339-1346.
[48] R. P. Herrera, V. Sgarzani, L. Bernardi, A. Ricci. Catalytic EnantioselectiveFriedel–Crafts Alkylation of Indoles with Nitroalkenes by Using a SimpleThiourea Organocatalyst[J].Angew.Chem., Int. Ed.,2005,44,6576-6579.
[49] M. Ganesh, D. Seidel. Catalytic Enantioselective Additions of Indoles toNitroalkenes[J].J. Am. Chem. Soc.,2008,130,16464-16465.
[50] E. M. Fleming, T. McCabe, S. J. Connon. Novel axially chiral bis-arylthiourea-based organocatalysts for asymmetric Friedel–Crafts type reactions[J].Tetrahedron Lett.,2006,47,7037-7042.
[51] W. Zhuang, R. G. Hazell, K. A. J rgensen. Enantioselective Friedel–Craftstype addition of indoles to nitro-olefins using a chiral hydrogen-bondingcatalyst-synthesis of optically active tetrahydro-β-carbolines[J].Org. Biomol.Chem.,2005,3,2566-2571.
[52] J. Itoh, K. Fuchibe, T. Akiyama. Chiral Phosphoric Acid CatalyzedEnantioselective Friedel–Crafts Alkylation of Indoles with Nitroalkenes:Cooperative Effect of3Molecular Sieves[J].Angew. Chem., Int. Ed.,2008,47,4016-4018.
[53] F.-L. Sun, M. Zeng, Q. Gu, S.-L. You. Enantioselective Synthesis of FluoreneDerivatives by Chiral Phosphoric Acid Catalyzed Tandem Double Friedel–Crafts Reaction[J].Chem. Eur. J.,2009,15,8709-8712.
[54] Shou-Guo Wang, Long Han, Mi Zeng, Feng-Lai Sun, Wei Zhang, Shu-Li You.Enantioselective synthesis of fluorene derivatives by chiral N-triflyl-phosphoramide catalyzed double Friedel–Crafts alkylation reaction[J].Org.Biomol. Chem.,2012,10,3202-3209.
[55] J. Nie, G. W. Zhang, L. Wang, A. P. Fu, Y. Zheng, J. A. Ma. A perfect doublerole of CF3groups in activating substrates and stabilizing adducts: the chiralBr nsted acid-catalyzed direct arylation of trifluoromethyl ketones[J].Chem.Commun.,2009,2356-2358.
[56] H. Li, Y.-Q. Wang, L. Deng. Enantioselective Friedel Crafts Reaction ofIndoles with Carbonyl Compounds Catalyzed by Bifunctional CinchonaAlkaloids[J].Org. Lett.,2006,8,4063-4065.
[57] Jing Deng, Shilei Zhang, Peng Ding, Hualiang Jiang, Wei Wang, Jian Li.Facile Creation of3-Indolyl-3-hydroxy-2-oxindoles by an OrganocatalyticEnantioselective Friedel–Crafts Reaction of Indoles with Isatins[J].Adv. Synth.Catal.,2010,352,833-838.
[58] H.-M. Dong, H.-H. Lu, L.-Q. Lu, C.-B. Chen, W.-J. Xiao. AsymmetricFriedel–Crafts Alkylations of Indoles with Ethyl Glyoxylate Catalyzed by(S)-BINOL-Titanium(IV) Complex: Direct Access to EnantiomericallyEnriched3-Indolyl(hydroxy)acetates[J].Adv. Synth. Catal.,2007,349,1597-1603.
[59] Béla T r k, Mohammed Abid, Gábor London, Joseph Esquibel, MariannaT r k, Shilpa C. Mhadgut, Ping Yan, G. K. Surya Prakash. HighlyEnantioselective Organocatalytic Hydroxyalkylation of Indoles with EthylTrifluoropyruvate[J].Angew. Chem. Int. Ed.,2005,44,3086-3089.
[60] W. Zhuang, N. Gathergood, R. G. Hazell, K. A. J rgensen. Catalytic, HighlyEnantioselective Friedel Crafts Reactions of Aromatic and HeteroaromaticCompounds to Trifluoropyruvate. A Simple Approach for the Formation ofOptically Active Aromatic and Heteroaromatic Hydroxy TrifluoromethylEsters[J].J. Org. Chem.,2001,66,1009-1013.
[61] Wataru Kashikura, Junji Itoh, Keiji Mori, Takahiko Akiyama. EnantioselectiveFriedel–Crafts Alkylation of Indoles, Pyrroles, and Furans with Trifluoro-pyruvate Catalyzed by Chiral Phosphoric Acid[J].Chem. Asian J.,2010,5,470-472.
[62] Y.-X. Jia, J. Zhong, S.-F. Zhu, C.-M. Zhang, Q.-L. Zhou. Chiral Br nsted AcidCatalyzed Enantioselective Friedel–Crafts Reaction of Indoles and α-ArylEnamides: Construction of Quaternary Carbon Atoms[J].Angew. Chem. Int. Ed.,2007,46,5565-5567.
[63] M. Terada, S. Yokoyama, K. Sorimachi, D. Uraguchi. Chiral PhosphoricAcid-Catalyzed Enantioselective Aza-Friedel–Crafts Reaction of Indoles[J].Adv.Synth. Catal.,2007,349,1863-1867.
[64] M. Terada, K. Sorimachi. Enantioselective Friedel Crafts Reaction ofElectron-Rich Alkenes Catalyzed by Chiral Br nsted Acid[J].J. Am. Chem. Soc.,2007,129,292-293.
[65] Q. Kang, Z.-A. Zhao, S.-L. You. Highly Enantioselective Friedel CraftsReaction of Indoles with Imines by a Chiral Phosphoric Acid[J].J. Am. Chem.Soc.,2007,129,1484-1485.
[66] Fangxi Xu, Dan Huang, Chao Han, Wei Shen, Xufeng Lin, Yanguang Wang.SPINOL-Derived Phosphoric Acids: Synthesis and Application in Enantio-selective Friedel-Crafts Reaction of Indoles with Imines[J].J. Org. Chem.,2010,75,8677–8680.
[67] Ling-Yan Chen, Hao He, Wing-Hong Chan, Albert W. M. Lee. ChiralSulfonimide as a Br nsted Acid Organocatalyst for Asymmetric Friedel-CraftsAlkylation of Indoles with Imines[J].J. Org. Chem.,2011,76,7141–7147.
[68] Y.-Q. Wang, J. Song, R. Hong, H. Li, L. Deng. Asymmetric Friedel CraftsReaction of Indoles with Imines by an Organic Catalyst[J].J. Am. Chem. Soc.,2006,128,8156-8157.
[69] P. Yu, J. He, C. X. Guo.9-Thiourea Cinchona alkaloid supported onmesoporous silica as a highly enantioselective, recyclable heterogeneousasymmetric catalyst[J].Chem. Commun.,2008,2355-2357.
[70] P. Yu, J. He, L. Yang, M. Pu, X. Guo. Stepwise fabrication and architecture ofheterogeneous9-thiourea epiquinine catalyst with excellent enantioselectivityin the asymmetric Friedel–Crafts reaction of indoles with imines[J].J. Catal.,2008,260,81-85.
[71] Yong Qian, Gaoyuan Ma, Aifeng Lv, Hai-Liang Zhu, Jing Zhao, Viresh H.Rawal. Squaramide-catalyzed enantioselective Friedel–Crafts reactionof indoleswith imines[J].Chem. Commun.,2010,46,3004–3006.
[72] Martin J. Wanner, Peter Hauwert, Hans E. Schoemaker, René de Gelder, Jan H.van Maarseveen, Henk Hiemstra. Synthesis of Enantiopure (S)-Indolylglycineby Organocatalyzed Friedel–Crafts Alkylation of Indole[J].Eur. J. Org. Chem.,2008,2008,180-185.
[73] Q. Kang, Z.-A. Zhao, S.-L. You. Enantioselective synthesis of (3-indolyl)-glycine derivatives via asymmetric Friedel–Crafts reaction between indoles andglyoxylate imines[J].Tetrahedron,2009,65,1603-1607.
[74] G. B. Rowland, E. B. Rowland, Y. Liang, J. A. Perman, J. C. Antilla. TheHighly Enantioselective Addition of Indoles to N-Acyl Imines with Use of aChiral Phosphoric Acid Catalyst[J].Org. Lett.,2007,9,2609-2611.
[75] Ralph Husmann, Erli Sugiono, Stefanie Mersmann, Gerhard Raabe, MagnusRueping, Carsten Bolm. Enantioselective Organocatalytic Synthesis ofQuaternary α-Amino Acids Bearing a CF3Moiety[J].Org. Lett.,2011,13,1044-1047.
[76] Magnus Rueping, Sadiya Raja, Alberto Nú ez. Asymmetric Br nstedAcid-Catalyzed Friedel–Crafts Reactions of Indoles with Cyclic Imines-Efficient Generation of Nitrogen-Substituted Quaternary Carbon Centers[J].Adv. Synth. Catal.,2011,353,563-568.
[77] Y.-X. Jia, J.-H. Xie, H.-F. Duan, L.-X. Wang, Q.-L. Zhou. AsymmetricFriedel Crafts Addition of Indoles to N-Sulfonyl Aldimines: A SimpleApproach to Optically Active3-Indolyl-methanamine Derivatives[J].Org. Lett.,2006,8,1621–1624.
[78] E. A. Peterson and E. N. Jacobsen. Enantioselective, Thiourea-CatalyzedIntermolecular Addition of Indoles to Cyclic N-Acyl Iminium Ions[J].Angew.Chem. Int. Ed.,2009,48,6328-6331.
[79] M. Rueping, B. J. Nachtsheim. Asymmetric Br nsted Acid CatalyzedNucleophilic Addition to in situ Generated Chiral N-Acyliminium Ions [J].Synlett,2010,119-122.
[80] Xiaolei Yu, Aidang Lu, Youming Wang, Guiping Wu, Haibin Song,Zhenghong Zhou, Chuchi Tang. Chiral Phosphoric Acid CatalyzedAsymmetric Friedel–Crafts Alkylation ofIndole with3-Hydroxyisoindolin-1-one: Enantioselective Synthesis of3-Indolyl-Substituted Isoindolin-1-ones[J].Eur. J. Org. Chem.,2011,892–897.
[81] G.-W. Zhang, L. Wang, J. Nie, J.-A. Ma. Chiral Br nsted Acid-MediatedEnantioselective Organocatalytic Three-Component Reaction for theConstruction of Trifluoromethyl-Containing Molecules[J].Adv. Synth. Catal.,2008,350,1457-1463.
[82] J. F. Austin, S. G. Kim, C. J. Sinz, W. J. Xiao, D. W. C. MacMillan.Enantioselective organocatalytic construction of pyrroloindolines by a cascadeaddition–cyclization strategy: Synthesis of (–)-flustramine B[J].Proc. Natl.Acad. Sci. U. S. A.,2004,101,5482-5487.
[83] S. B. Jones, B. Simmons, D. W. C. MacMillan. Nine-Step EnantioselectiveTotal Synthesis of (+)-Minfiensine[J].J. Am. Chem.Soc.,2009,131,13606-13607.
[84] Y. Huang, A. M. Walji, C. H. Larsen, D. W. C. MacMillan. EnantioselectiveOrgano-Cascade Catalysis[J].J. Am. Chem. Soc.,2005,127,15051-15053.
[85] Dieter Enders, Arun A. Narine, Fabien Toulgoat, Tom Bisschops. AsymmetricBr nsted Acid Catalyzed Isoindoline Synthesis:Enhancement of EnantiomericRatio by Stereoablative Kinetic Resolution[J].Angew. Chem. Int. Ed.,2008,47,5661-5665.
[86] Biao Xu, Zhi-Lei Guo, Wan-Yan Jin, Zhi-Ping Wang, Yun-Gui Peng, Qi-XiangGuo. Multistep One-Pot Synthesis of Enantioenriched PolysubstitutedCyclopenta[b]indoles[J].Angew. Chem. Int. Ed.,2012,51,1059-1062.
[87] Nick A. Paras, David W. C. MacMillan. New Strategies in Organic Catalysis:The First Enantioselective Organocatalytic Friedel-Crafts Alkylation[J].J. Am.Chem. Soc.,2001,123,4370-4371.
[88] Bianca F. Bonini, Elena Capitò, Mauro Comes-Franchini, MariafrancescaFochi, Alfredo Riccia, Binne Zwanenburg. Aziridin-2-yl methanols asorganocatalysts in Diels–Alder reactions and Friedel–Crafts alkylations ofN-methyl-pyrrole and N-methyl-indole[J].Tetrahedron: Asymmetry,2006,17,3135–3143.
[89] Xianrui Liang, Jiaoyang Fan, Fei Shi, Weike Su. Imidazolethiones: novel andefficient organocatalysts for asymmetric Friedel–Crafts alkylation[J].Tetrahedron Letters,2010,51,2505–2507.
[90] Yi-Fei Sheng, Qing Gu, An-Jiang Zhang, Shu-Li You. Chiral Br nstedAcid-Catalyzed AsymmetricFriedel-Crafts Alkylation of Pyrroles withNitroolefins[J].J. Org. Chem.,2009,74,6899–6901.
[91] Guilong Li, Gerald B. Rowland, Emily B. Rowland, Jon C. Antilla.Organocatalytic Enantioselective Friedel-Crafts Reaction of Pyrrole Derivativeswith Imines[J].Org. Lett.,2007,9,4065-4068.
[92] Shuichi Nakamura, Yuki Sakurai, Hiroki Nakashima, Norio Shibata, TakeshiToru. Organocatalytic Enantioselective Aza-Friedel–Crafts Alkylation ofPyrroles with N-(Heteroarenesulfonyl)imines[J].Synlett,2009,10,1639–1642.
[93] Manabu Hatano, Yoshihiro Sugiura, Matsujiro Akakura, Kazuaki Ishihara.Enantioselective Friedel–Crafts Aminoalkylation Catalyzed by ChiralAmmonium1,1’-Binaphthyl-2,2’-disulfonates[J].Synlett,2011,9,1247–1250.
[94] T. Akiyama, J. Itoh, K. Yokota, K. Fuchibe. Enantioselective Mannich-TypeReaction Catalyzed by a Chiral Br nsted Acid[J].Angew. Chem. Int. Ed.,2004,43,1566-1568.
[95] D. Uraguchi, M. Terada. Chiral Br nsted Acid-Catalyzed Direct MannichReactions via Electrophilic Activation[J].J. Am. Chem. Soc.,2004,126,5356-5357.
[96] Takahiko Akiyama, Youichi Saitoh, Hisashi Morita, Kohei Fuchibe.Enantioselective Mannich-Type Reaction Catalyzed by a Chiral Br nsted AcidDerived from TADDOL[J].Adv. Synth. Catal.,2005,347,1523-1526.
[97] Xiao-Hua Chen, Xiao-Ying Xu, Hua Liu, Lin-Feng Cun, Liu-Zhu Gong.Highly Enantioselective Organocatalytic Biginelli Reaction[J].J. Am. Chem.Soc.,2006,128,14802-14803.
[98] G. B. Rowland, H. Zhang, E. B. Rowland, S. Chennamadhavuni,Y. Wang, J. C.Antilla. Br nsted Acid-Catalyzed Imine Amidation[J].J. Am. Chem. Soc.,2005,127,15696-15697.
[99] D. Nakashima, H. Yamamoto. Design of Chiral N-Triflyl Phosphoramide as aStrong Chiral Br nsted Acid and Its Application to Asymmetric Diels AlderReaction[J].J. Am. Chem. Soc.,2006,128,9626-9627.
[100] V. N. Wakchaure, B. List. A New Structural Motif for Bifunctional Br nstedAcid/Base Organocatalysis[J].Angew. Chem. Int. Ed.,2010,49,4136-4139.
[101] Sreekumar Vellalath, Ilija ori, Benjamin List. N-Phosphinyl Phosphoramide—A Chiral Br nsted Acid Motif for the Direct Asymmetric N,O-Acetalizationof Aldehydes[J].Angew.Chem. Int. Ed.,2010,49,9749-9752.
[102] Ilija ori, Benjamin List. Asymmetric spiroacetalization catalysed by confinedBr nsted acids[J].Nature,2012,483,315-319.
[103] S. Liao, I. ori, Q. Wang, B. List. Activation of H2O2by Chiral ConfinedBr nsted Acids: A Highly Enantioselective Catalytic Sulfoxidation[J].J. Am.Chem. Soc.,2012,134,10765-10768.
[104] Ying-Ying Chen, Yi-Jun Jiang, Yan-Sen Fan, Di Sha, Qifeng Wang,Guangliang Zhang, Liangyu Zheng, Suoqin Zhang. Double axially chiralbisphosphorylimides as novel Br nsted acids in asymmetric three-componentMannich reaction[J].Tetrahedron: Asymmetry,2012,23,904-909.
[105] Zhensheng Ding. VANOL and VAPOL Chemistry: New Methodologies, LargeScale Synthesis, Derivatives, and Synthetic Applications[D].Michigan StateUniversity,2009.
[106] Hitoshi Ube, Satoko Fukuchi, Masahiro Terada. Enantioselective aza-Friedel–Crafts reaction catalyzed by a water inclusion complex of O,O’-diacyltartaric acid[J].Tetrahedron: Asymmetry,2010,21,1203–1205.
[107] Jonathan T. Reeves, Zhulin Tan, Zhengxu S. Han, Guisheng Li, Yongda Zhang,Yibo Xu,Diana C. Reeves, Nina C. Gonnella, Shengli Ma, Heewon Lee, BruceZ. Lu, Chris H. Senanayake. Direct Titanium-Mediated Conversion of Ketonesinto Enamides withAmmonia and Acetic Anhydride[J].Angew. Chem. Int. Ed.,2012,51,1400–1404.
[2] Giuseppe Bartoli, Giorgio Bencivenni, Renato Dalpozzo. Organocatalyticstrategies for the asymmetric functionalization of indoles[J].Chem. Soc. Rev.,2010,39,4449-4465.
[3] Joel F. Austin, David W. C. MacMillan. Enantioselective OrganocatalyticIndole Alkylations. Design of a New and Highly Effective Chiral Amine forIminium Catalysis[J].J. Am. Chem. Soc.,2002,124,1172-1173.
[4] Sung-Gon Kim. Organocatalytic Asymmetric Friedel-Crafts Alkylation toγ-Hydroxy α,β-Unsaturated Aldehyde[J].Bull. Korean Chem. Soc.,2009,30,2519-2520.
[5] Stephen Hanessian, Eli Stoffman, Xueling Mi, Paul Renton. Applications ofOrganocatalytic Asymmetric Synthesis to Drug Prototypes-Dual Action andSelective Inhibitors of n-Nitric Oxide Synthase with Activity Against the5-HT1D/1BSubreceptors[J].Org. Lett.,2011,13,840-843.
[6] Chang-Feng Li, Hiu Liu, Jie Liao, Yi-Ju Cao, Xiao-Peng Liu, Wen-Jing Xiao.Enantioselective Organocatalytic Intramolecular Ring-Closing Friedel-Crafts-Type Alkylation of Indoles[J].Org. Lett.,2007,9,1847-1850.
[7] Ying-Cen Guo, Dong-Ping Li, Yu-Ling Li, Hong-Mei Wang, Wen-Jing Xiao.Asymmetric Friedel-Crafts Alkylations of Indoles with Dialkyl3-Oxoprop-1-enylphosphonates: Organocatalytic Enantioselective Synthesis of α-IndolylPhosphonates[J].Chirality,2009,21,777-785.
[8] H. Dalton King, Zhaoxing Meng, Derek Denhart, Ronald Mattson, Roy Kimura,Dedong Wu, Qi Gao, John E. Macor. Enantioselective Synthesis of a HighlyPotent Selective Serotonin Reuptake Inhibitor. An Application of Imidazolidin-one Catalysis to the Alkylation of Indoles with an α,β-Disubstituted α,β-Unsaturated Aldehyde[J].Org. Lett.,2005,7,3437-3440.
[9] Mauro Marigo, Tobias C. Wabnitz, Doris Fielenbach, Karl Anker J rgensen.Enantioselective Organocatalyzed a Sulfenylation of Aldehydes[J].Angew.Chem. Int. Ed.,2005,44,794-797.
[10] Yujiro Hayashi, Hiroaki Gotoh, Takaaki Hayashi, Mitsuru Shoji.Diphenylprolinol Silyl Ethers as Efficient Organocatalysts for the AsymmetricMichael Reaction of Aldehydes and Nitroalkenes[J].Angew. Chem. Int. Ed.,2005,44,4212-4215.
[11] A. Lattanzi. α,α-Diarylprolinols: bifunctional organocatalysts for asymmetricsynthesis[J].Chem. Commun.,2009,1452–1463.
[12] A. Mielgo, C. Palomo. α,α-Diarylprolinol Ethers: New Tools forFunctionalization of Carbonyl Compounds[J].Chem.Asian J.,2008,3,922-948.
[13] Zhi-Jing Wang, Jian-Guo Yang, Jun Jin, Xin Lv, Weiliang Bao. Enantio-selective Friedel–Crafts alkylation of indoles with aromatic α,β-unsaturatedaldehydes catalyzed by diphenylprolinol silyl ether[J].Synthesis,2009,23,3994-4000.
[14] H. Liang, W. Lei, C. Chao, Z. Bangzhi and R. Wang. An Efficient Enantio-selective Method for Asymmetric Friedel–Crafts Alkylation of Indoles withα,β-Unsaturated Aldehydes[J].Adv. Synth. Catal.,2009,351,772–778.
[15] Yi-Ju Cao, Hong-Gang Cheng, Liang-Qiu Lu, Ji-Ji Zhang, Ying Cheng,Jia-Rong Chen, Wen-Jing Xiao.Organocatalytic Multiple Cascade Reactions: ANew Strategy for the Construction of Enantioenriched Tetrahydrocarbazoles[J].Adv. Synth. Catal.,2011,353,617-623.
[16] Xiao-Yu Zhu, Xiao-Lei An, Chang-Feng Li, Fu-Gen Zhang, Qiu-Lin Hua,Jia-Rong Chen, Wen-Jing Xiao. A Practical and Enantioselective Approach toTetrahydrocarbazoles by Asymmetric Organocatalysis[J].ChemCatChem,2011,3,679-683.
[17] Kazutaka Shibatomi, Akira Narayama, Yoshiyuki Abe, Seiji Iwasa. Practicalsynthesis of4,4,4-trifluorocrotonaldehyde: a versatile precursor for theenantioselective formation of trifluoromethylated stereogenic centers viaorganocatalytic1,4-additions[J].Chem. Commun.,2012,48,7380–7382.
[18] Tian Tian, Baojian Pei, Qinghua Li, Hao He, Ling-Yan Chen, Xiang Zhou,Wing-Hong Chan, Albert W. M. Lee. CaSH Organocatalysis: Ena ntioselectiveFriedel–Crafts Alkylation of Indoles with α,β-unsaturated aldehydes[J].Synlett.,2009,13,2115-2118.
[19] K. Akagawa, T. Yamashita, S. Sakamoto and K. Kudo. Friedel–Crafts-typealkylation in aqueous media using resin-supported peptide catalyst havingpolyleucine[J].Tetrahedron Lett.,2009,50,5602-5604.
[20] Thomas B. Poulsen, Karl Anker J rgensen. Catalytic Asymmetric FriedelCrafts Alkylation Reactions Copper Showed the Way[J].Chem. Rev.,2008,108,2903-2915.
[21] M. Bandini, A. Melloni, A. Umani-Ronchi. New Catalytic Approaches in theStereoselective Friedel–Crafts Alkylation Reaction[J].Angew.Chem.Int.Ed.,2004,43,550-556.
[22] M. Bandini, A. Eichholzer, A. Umani-Ronchi. An Update on CatalyticEnantioselective Alkylations of Indoles[J].Mini-Rev.Org.Chem.,2007,4,115-124.
[23] D. P. Li, Y. C. Guo, Y. Ding, W. J. Xiao. Chem. Organocatalytic C3-selectiveFriedel–Crafts alkylations of indoles with α,β-unsaturated ketones[J].Chem.Commun.,2006,799-801.
[24] W. Zhou, L.-W. Xu, L. Li, L. Yang, C.-G. Xia. Enantioselective Michael-TypeFriedel-Crafts Reactions of Indoles to Enones Catalyzed by a ChiralCamphor-Based Br nsted Acid[J].Eur. J. Org.Chem.,2006,23,5225-5227.
[25] W. Chen, W. Du, L. Yue, R. Li, Y. Wu, L. S. Ding, Y. C. Chen.Organocatalytic enantioselective indole alkylations of α,β-unsaturated ketones[J].Org. Biomol. Chem.,2007,5,816-821.
[26] G. Blay, I. Fernandez, J. R. Pedro, C. Vila. Highly EnantioselectiveFriedel Crafts Alkylations of Indoles with Simple Enones Catalyzed byZirconium(IV) BINOL Complexes[J].Org. Lett.,2007,9,2601-2604.
[27] G. Bartoli, M. Bosco, A. Carlone, F. Pesciaioli, L. Sambri, P. Melchiorre.Organocatalytic Asymmetric Friedel Crafts Alkylation of Indoles with Simpleα,β-Unsaturated Ketones[J].Org. Lett.,2007,9,1403-1405.
[28] P. Ricci, A. Carlone, G. Bartoli, M. Bosco, L. Sambri, P. Melchiorre.Organocatalytic Asymmetric Sulfa-Michael Addition to α,β-UnsaturatedKetones[J].Adv. Synth. Catal.,2008,350,49-53.
[29] F. Pesciaioli, F. De Vincentiis, P. Galzerano, G. Bencivenni,G. Bartoli, A.Mazzanti, P. Melchiorre. Organocatalytic Asymmetric Aziridination of Enones[J].Angew. Chem. Int. Ed.,2008,47,8703-8706.
[30] M. Rueping, B. J. Nachtsheim, S. A. Moreth, M. Bolte. Asymmetric Br nstedAcid Catalysis: Enantioselective Nucleophilic Substitutions and1,4-Additions[J].Angew. Chem. Int. Ed.,2008,47,593-596.
[31] Chun-Hui Xing, Yuan-Xi Liao, Jaclynn Ng, Qiao-Sheng Hu. Optically Active1,1’-Spirobiindane-7,7’-diol (SPINOL)-Based Phosphoric Acids as HighlyEnantioselective Catalysts for Asymmetric Organocatalysis[J].J. Org. Chem.,2011,76,4125–4131.
[32] H.-Y. Tang, A.-D. Lu, Z.-H. Zhou, G.-F. Zhao, L.-N. He, C.-C. Tang. ChiralPhosphoric Acid Catalyzed Asymmetric Friedel–Crafts Alkylation of Indoleswith Simple α,β-Unsaturated Aromatic Ketones[J].Eur. J. Org. Chem.,2008,1406-1410.
[33] A. Scettri, R. Villano, M. Acocella. Asymmetric Friedel-Crafts Alkylation ofIndole with Chalcones Catalyzed by Chiral Phosphoric Acids[J].Molecules,2009,14,3030-3036.
[34] Tsubasa Sakamoto, Junji Itoh, Keiji Mori, Takahiko Akiyama. Chiral Br nstedacid catalyzed asymmetric Friedel–Crafts alkylation reaction of indoles withα,β-unsaturated ketones: short access to optically active2-and3-substitutedindole derivatives[J].Org. Biomol. Chem.,2010,8,5448–5454.
[35] Q. Cai, Z.-A. Zhao, S.-L. You. Asymmetric Construction of Polycyclic Indolesthrough Olefin Cross-Metathesis/Intramolecular Friedel–Crafts Alkylationunder Sequential Catalysis[J].Angew. Chem. Int. Ed.,2009,48,7428-7431.
[36] Jun-Wei Zhang, Quan Cai, Xiao-Xin Shi, Wei Zhang, Shu-Li You.Enantioselective Synthesis of Tetrahydropyrano[3,4-b]indoles Catalyzed byChiral N-Triflyl Phosphoramide via Intramolecular Friedel–Crafts AlkylationReaction[J].Synlett,2011,9,1239–1242.
[37] Zeng-kai Pei, Yan Zheng, Jing Nie, Jun-An Ma. Chiral Br nsted acid-catalyzedregio-and enantioselective arylation of α,β-unsaturated trifluoromethyl ketones[J].Tetrahedron Letters,2010,51,4658-4661.
[38] Prabhakar Bachu, Takahiko Akiyama. Enantioselective Friedel–Craftsalkylation reaction of indoles with α,β-unsaturated acyl phosphonates catalyzedby chiral phosphoric acid[J].Chem. Commun.,2010,46,4112–4114.
[39] S. Adachi, F. Tanaka, K. Watanabe, T. Harada. Oxazaborolidinone-CatalyzedEnantioselective Friedel Crafts Alkylation of Furans and Indoles withα,β-Unsaturated Ketones[J].Org. Lett.,2009,11,5206-5209.
[40] T. Arai, N. Yokoyama. Tandem Catalytic Asymmetric Friedel–Crafts/HenryReaction: Control of Three Contiguous Acyclic Stereocenters[J].Angew. Chem.Int. Ed.,2008,47,4989-4992.
[41] Y.-X. Jia, S.-F. Zhu, Y. Yang, Q.-L. Zhou. Asymmetric Friedel CraftsAlkylations of Indoles with Nitroalkenes Catalyzed by Zn(II) BisoxazolineComplexes[J].J. Org. Chem.,2006,71,75-80.
[42] P. K. Singh, A. Bisai, V. K. Singh. Enantioselective Friedel–Crafts alkylationof indoles with nitroalkenes catalyzed by a bis(oxazoline)–Cu(II) complex[J].Tetrahedron Lett.,2007,48,1127-1129.
[43] Y. Sui, L. Liu, J.-L. Zhao, D. Wang, Y.-J. Chen. Catalytic and asymmetricFriedel–Crafts alkylation of indoles with nitroacrylates. Application to thesynthesis of tryptophan analogues[J].Tetrahedron,2007,63,5173-5183.
[44] H. Liu, S.-F. Lu, J. Xu, D.-M. Du. Asymmetric Friedel–Crafts Alkylation ofElectron-Rich N-Heterocycles with Nitroalkenes Catalyzed by Diphenylamine-Tethered Bis(oxazoline) and Bis(thiazoline) ZnIIComplexes[J].Chem.Asian J.,2008,3,1111-1121.
[45] Seán C. McKeon, Helge Müller-Bunz, Patrick J. Guiry. New Thiazoline–Oxazoline Ligands and Their Application in the Asymmetric Friedel–CraftsReaction[J].Eur. J. Org. Chem.,2009,4833-4841.
[46] M. Bandini, A. Garelli, M. Rovinetti, S. Tommasi, A. Umani-Ronchi. Catalyticenantioselective addition of indoles to arylnitroalkenes: An effective route toenantiomerically enriched tryptamine precursors[J].Chirality,2005,17,522-529.
[47] Z.-L. Yuan, Z.-Y. Lei, M. Shi. BINAM and H8-BINAM-based chiral iminesand Zn(OTf)2-catalyzed enantioselective Friedel–Crafts alkylation of indoleswith nitroalkenes[J].Tetrahedron:Asymmetry,2008,19,1339-1346.
[48] R. P. Herrera, V. Sgarzani, L. Bernardi, A. Ricci. Catalytic EnantioselectiveFriedel–Crafts Alkylation of Indoles with Nitroalkenes by Using a SimpleThiourea Organocatalyst[J].Angew.Chem., Int. Ed.,2005,44,6576-6579.
[49] M. Ganesh, D. Seidel. Catalytic Enantioselective Additions of Indoles toNitroalkenes[J].J. Am. Chem. Soc.,2008,130,16464-16465.
[50] E. M. Fleming, T. McCabe, S. J. Connon. Novel axially chiral bis-arylthiourea-based organocatalysts for asymmetric Friedel–Crafts type reactions[J].Tetrahedron Lett.,2006,47,7037-7042.
[51] W. Zhuang, R. G. Hazell, K. A. J rgensen. Enantioselective Friedel–Craftstype addition of indoles to nitro-olefins using a chiral hydrogen-bondingcatalyst-synthesis of optically active tetrahydro-β-carbolines[J].Org. Biomol.Chem.,2005,3,2566-2571.
[52] J. Itoh, K. Fuchibe, T. Akiyama. Chiral Phosphoric Acid CatalyzedEnantioselective Friedel–Crafts Alkylation of Indoles with Nitroalkenes:Cooperative Effect of3Molecular Sieves[J].Angew. Chem., Int. Ed.,2008,47,4016-4018.
[53] F.-L. Sun, M. Zeng, Q. Gu, S.-L. You. Enantioselective Synthesis of FluoreneDerivatives by Chiral Phosphoric Acid Catalyzed Tandem Double Friedel–Crafts Reaction[J].Chem. Eur. J.,2009,15,8709-8712.
[54] Shou-Guo Wang, Long Han, Mi Zeng, Feng-Lai Sun, Wei Zhang, Shu-Li You.Enantioselective synthesis of fluorene derivatives by chiral N-triflyl-phosphoramide catalyzed double Friedel–Crafts alkylation reaction[J].Org.Biomol. Chem.,2012,10,3202-3209.
[55] J. Nie, G. W. Zhang, L. Wang, A. P. Fu, Y. Zheng, J. A. Ma. A perfect doublerole of CF3groups in activating substrates and stabilizing adducts: the chiralBr nsted acid-catalyzed direct arylation of trifluoromethyl ketones[J].Chem.Commun.,2009,2356-2358.
[56] H. Li, Y.-Q. Wang, L. Deng. Enantioselective Friedel Crafts Reaction ofIndoles with Carbonyl Compounds Catalyzed by Bifunctional CinchonaAlkaloids[J].Org. Lett.,2006,8,4063-4065.
[57] Jing Deng, Shilei Zhang, Peng Ding, Hualiang Jiang, Wei Wang, Jian Li.Facile Creation of3-Indolyl-3-hydroxy-2-oxindoles by an OrganocatalyticEnantioselective Friedel–Crafts Reaction of Indoles with Isatins[J].Adv. Synth.Catal.,2010,352,833-838.
[58] H.-M. Dong, H.-H. Lu, L.-Q. Lu, C.-B. Chen, W.-J. Xiao. AsymmetricFriedel–Crafts Alkylations of Indoles with Ethyl Glyoxylate Catalyzed by(S)-BINOL-Titanium(IV) Complex: Direct Access to EnantiomericallyEnriched3-Indolyl(hydroxy)acetates[J].Adv. Synth. Catal.,2007,349,1597-1603.
[59] Béla T r k, Mohammed Abid, Gábor London, Joseph Esquibel, MariannaT r k, Shilpa C. Mhadgut, Ping Yan, G. K. Surya Prakash. HighlyEnantioselective Organocatalytic Hydroxyalkylation of Indoles with EthylTrifluoropyruvate[J].Angew. Chem. Int. Ed.,2005,44,3086-3089.
[60] W. Zhuang, N. Gathergood, R. G. Hazell, K. A. J rgensen. Catalytic, HighlyEnantioselective Friedel Crafts Reactions of Aromatic and HeteroaromaticCompounds to Trifluoropyruvate. A Simple Approach for the Formation ofOptically Active Aromatic and Heteroaromatic Hydroxy TrifluoromethylEsters[J].J. Org. Chem.,2001,66,1009-1013.
[61] Wataru Kashikura, Junji Itoh, Keiji Mori, Takahiko Akiyama. EnantioselectiveFriedel–Crafts Alkylation of Indoles, Pyrroles, and Furans with Trifluoro-pyruvate Catalyzed by Chiral Phosphoric Acid[J].Chem. Asian J.,2010,5,470-472.
[62] Y.-X. Jia, J. Zhong, S.-F. Zhu, C.-M. Zhang, Q.-L. Zhou. Chiral Br nsted AcidCatalyzed Enantioselective Friedel–Crafts Reaction of Indoles and α-ArylEnamides: Construction of Quaternary Carbon Atoms[J].Angew. Chem. Int. Ed.,2007,46,5565-5567.
[63] M. Terada, S. Yokoyama, K. Sorimachi, D. Uraguchi. Chiral PhosphoricAcid-Catalyzed Enantioselective Aza-Friedel–Crafts Reaction of Indoles[J].Adv.Synth. Catal.,2007,349,1863-1867.
[64] M. Terada, K. Sorimachi. Enantioselective Friedel Crafts Reaction ofElectron-Rich Alkenes Catalyzed by Chiral Br nsted Acid[J].J. Am. Chem. Soc.,2007,129,292-293.
[65] Q. Kang, Z.-A. Zhao, S.-L. You. Highly Enantioselective Friedel CraftsReaction of Indoles with Imines by a Chiral Phosphoric Acid[J].J. Am. Chem.Soc.,2007,129,1484-1485.
[66] Fangxi Xu, Dan Huang, Chao Han, Wei Shen, Xufeng Lin, Yanguang Wang.SPINOL-Derived Phosphoric Acids: Synthesis and Application in Enantio-selective Friedel-Crafts Reaction of Indoles with Imines[J].J. Org. Chem.,2010,75,8677–8680.
[67] Ling-Yan Chen, Hao He, Wing-Hong Chan, Albert W. M. Lee. ChiralSulfonimide as a Br nsted Acid Organocatalyst for Asymmetric Friedel-CraftsAlkylation of Indoles with Imines[J].J. Org. Chem.,2011,76,7141–7147.
[68] Y.-Q. Wang, J. Song, R. Hong, H. Li, L. Deng. Asymmetric Friedel CraftsReaction of Indoles with Imines by an Organic Catalyst[J].J. Am. Chem. Soc.,2006,128,8156-8157.
[69] P. Yu, J. He, C. X. Guo.9-Thiourea Cinchona alkaloid supported onmesoporous silica as a highly enantioselective, recyclable heterogeneousasymmetric catalyst[J].Chem. Commun.,2008,2355-2357.
[70] P. Yu, J. He, L. Yang, M. Pu, X. Guo. Stepwise fabrication and architecture ofheterogeneous9-thiourea epiquinine catalyst with excellent enantioselectivityin the asymmetric Friedel–Crafts reaction of indoles with imines[J].J. Catal.,2008,260,81-85.
[71] Yong Qian, Gaoyuan Ma, Aifeng Lv, Hai-Liang Zhu, Jing Zhao, Viresh H.Rawal. Squaramide-catalyzed enantioselective Friedel–Crafts reactionof indoleswith imines[J].Chem. Commun.,2010,46,3004–3006.
[72] Martin J. Wanner, Peter Hauwert, Hans E. Schoemaker, René de Gelder, Jan H.van Maarseveen, Henk Hiemstra. Synthesis of Enantiopure (S)-Indolylglycineby Organocatalyzed Friedel–Crafts Alkylation of Indole[J].Eur. J. Org. Chem.,2008,2008,180-185.
[73] Q. Kang, Z.-A. Zhao, S.-L. You. Enantioselective synthesis of (3-indolyl)-glycine derivatives via asymmetric Friedel–Crafts reaction between indoles andglyoxylate imines[J].Tetrahedron,2009,65,1603-1607.
[74] G. B. Rowland, E. B. Rowland, Y. Liang, J. A. Perman, J. C. Antilla. TheHighly Enantioselective Addition of Indoles to N-Acyl Imines with Use of aChiral Phosphoric Acid Catalyst[J].Org. Lett.,2007,9,2609-2611.
[75] Ralph Husmann, Erli Sugiono, Stefanie Mersmann, Gerhard Raabe, MagnusRueping, Carsten Bolm. Enantioselective Organocatalytic Synthesis ofQuaternary α-Amino Acids Bearing a CF3Moiety[J].Org. Lett.,2011,13,1044-1047.
[76] Magnus Rueping, Sadiya Raja, Alberto Nú ez. Asymmetric Br nstedAcid-Catalyzed Friedel–Crafts Reactions of Indoles with Cyclic Imines-Efficient Generation of Nitrogen-Substituted Quaternary Carbon Centers[J].Adv. Synth. Catal.,2011,353,563-568.
[77] Y.-X. Jia, J.-H. Xie, H.-F. Duan, L.-X. Wang, Q.-L. Zhou. AsymmetricFriedel Crafts Addition of Indoles to N-Sulfonyl Aldimines: A SimpleApproach to Optically Active3-Indolyl-methanamine Derivatives[J].Org. Lett.,2006,8,1621–1624.
[78] E. A. Peterson and E. N. Jacobsen. Enantioselective, Thiourea-CatalyzedIntermolecular Addition of Indoles to Cyclic N-Acyl Iminium Ions[J].Angew.Chem. Int. Ed.,2009,48,6328-6331.
[79] M. Rueping, B. J. Nachtsheim. Asymmetric Br nsted Acid CatalyzedNucleophilic Addition to in situ Generated Chiral N-Acyliminium Ions [J].Synlett,2010,119-122.
[80] Xiaolei Yu, Aidang Lu, Youming Wang, Guiping Wu, Haibin Song,Zhenghong Zhou, Chuchi Tang. Chiral Phosphoric Acid CatalyzedAsymmetric Friedel–Crafts Alkylation ofIndole with3-Hydroxyisoindolin-1-one: Enantioselective Synthesis of3-Indolyl-Substituted Isoindolin-1-ones[J].Eur. J. Org. Chem.,2011,892–897.
[81] G.-W. Zhang, L. Wang, J. Nie, J.-A. Ma. Chiral Br nsted Acid-MediatedEnantioselective Organocatalytic Three-Component Reaction for theConstruction of Trifluoromethyl-Containing Molecules[J].Adv. Synth. Catal.,2008,350,1457-1463.
[82] J. F. Austin, S. G. Kim, C. J. Sinz, W. J. Xiao, D. W. C. MacMillan.Enantioselective organocatalytic construction of pyrroloindolines by a cascadeaddition–cyclization strategy: Synthesis of (–)-flustramine B[J].Proc. Natl.Acad. Sci. U. S. A.,2004,101,5482-5487.
[83] S. B. Jones, B. Simmons, D. W. C. MacMillan. Nine-Step EnantioselectiveTotal Synthesis of (+)-Minfiensine[J].J. Am. Chem.Soc.,2009,131,13606-13607.
[84] Y. Huang, A. M. Walji, C. H. Larsen, D. W. C. MacMillan. EnantioselectiveOrgano-Cascade Catalysis[J].J. Am. Chem. Soc.,2005,127,15051-15053.
[85] Dieter Enders, Arun A. Narine, Fabien Toulgoat, Tom Bisschops. AsymmetricBr nsted Acid Catalyzed Isoindoline Synthesis:Enhancement of EnantiomericRatio by Stereoablative Kinetic Resolution[J].Angew. Chem. Int. Ed.,2008,47,5661-5665.
[86] Biao Xu, Zhi-Lei Guo, Wan-Yan Jin, Zhi-Ping Wang, Yun-Gui Peng, Qi-XiangGuo. Multistep One-Pot Synthesis of Enantioenriched PolysubstitutedCyclopenta[b]indoles[J].Angew. Chem. Int. Ed.,2012,51,1059-1062.
[87] Nick A. Paras, David W. C. MacMillan. New Strategies in Organic Catalysis:The First Enantioselective Organocatalytic Friedel-Crafts Alkylation[J].J. Am.Chem. Soc.,2001,123,4370-4371.
[88] Bianca F. Bonini, Elena Capitò, Mauro Comes-Franchini, MariafrancescaFochi, Alfredo Riccia, Binne Zwanenburg. Aziridin-2-yl methanols asorganocatalysts in Diels–Alder reactions and Friedel–Crafts alkylations ofN-methyl-pyrrole and N-methyl-indole[J].Tetrahedron: Asymmetry,2006,17,3135–3143.
[89] Xianrui Liang, Jiaoyang Fan, Fei Shi, Weike Su. Imidazolethiones: novel andefficient organocatalysts for asymmetric Friedel–Crafts alkylation[J].Tetrahedron Letters,2010,51,2505–2507.
[90] Yi-Fei Sheng, Qing Gu, An-Jiang Zhang, Shu-Li You. Chiral Br nstedAcid-Catalyzed AsymmetricFriedel-Crafts Alkylation of Pyrroles withNitroolefins[J].J. Org. Chem.,2009,74,6899–6901.
[91] Guilong Li, Gerald B. Rowland, Emily B. Rowland, Jon C. Antilla.Organocatalytic Enantioselective Friedel-Crafts Reaction of Pyrrole Derivativeswith Imines[J].Org. Lett.,2007,9,4065-4068.
[92] Shuichi Nakamura, Yuki Sakurai, Hiroki Nakashima, Norio Shibata, TakeshiToru. Organocatalytic Enantioselective Aza-Friedel–Crafts Alkylation ofPyrroles with N-(Heteroarenesulfonyl)imines[J].Synlett,2009,10,1639–1642.
[93] Manabu Hatano, Yoshihiro Sugiura, Matsujiro Akakura, Kazuaki Ishihara.Enantioselective Friedel–Crafts Aminoalkylation Catalyzed by ChiralAmmonium1,1’-Binaphthyl-2,2’-disulfonates[J].Synlett,2011,9,1247–1250.
[94] T. Akiyama, J. Itoh, K. Yokota, K. Fuchibe. Enantioselective Mannich-TypeReaction Catalyzed by a Chiral Br nsted Acid[J].Angew. Chem. Int. Ed.,2004,43,1566-1568.
[95] D. Uraguchi, M. Terada. Chiral Br nsted Acid-Catalyzed Direct MannichReactions via Electrophilic Activation[J].J. Am. Chem. Soc.,2004,126,5356-5357.
[96] Takahiko Akiyama, Youichi Saitoh, Hisashi Morita, Kohei Fuchibe.Enantioselective Mannich-Type Reaction Catalyzed by a Chiral Br nsted AcidDerived from TADDOL[J].Adv. Synth. Catal.,2005,347,1523-1526.
[97] Xiao-Hua Chen, Xiao-Ying Xu, Hua Liu, Lin-Feng Cun, Liu-Zhu Gong.Highly Enantioselective Organocatalytic Biginelli Reaction[J].J. Am. Chem.Soc.,2006,128,14802-14803.
[98] G. B. Rowland, H. Zhang, E. B. Rowland, S. Chennamadhavuni,Y. Wang, J. C.Antilla. Br nsted Acid-Catalyzed Imine Amidation[J].J. Am. Chem. Soc.,2005,127,15696-15697.
[99] D. Nakashima, H. Yamamoto. Design of Chiral N-Triflyl Phosphoramide as aStrong Chiral Br nsted Acid and Its Application to Asymmetric Diels AlderReaction[J].J. Am. Chem. Soc.,2006,128,9626-9627.
[100] V. N. Wakchaure, B. List. A New Structural Motif for Bifunctional Br nstedAcid/Base Organocatalysis[J].Angew. Chem. Int. Ed.,2010,49,4136-4139.
[101] Sreekumar Vellalath, Ilija ori, Benjamin List. N-Phosphinyl Phosphoramide—A Chiral Br nsted Acid Motif for the Direct Asymmetric N,O-Acetalizationof Aldehydes[J].Angew.Chem. Int. Ed.,2010,49,9749-9752.
[102] Ilija ori, Benjamin List. Asymmetric spiroacetalization catalysed by confinedBr nsted acids[J].Nature,2012,483,315-319.
[103] S. Liao, I. ori, Q. Wang, B. List. Activation of H2O2by Chiral ConfinedBr nsted Acids: A Highly Enantioselective Catalytic Sulfoxidation[J].J. Am.Chem. Soc.,2012,134,10765-10768.
[104] Ying-Ying Chen, Yi-Jun Jiang, Yan-Sen Fan, Di Sha, Qifeng Wang,Guangliang Zhang, Liangyu Zheng, Suoqin Zhang. Double axially chiralbisphosphorylimides as novel Br nsted acids in asymmetric three-componentMannich reaction[J].Tetrahedron: Asymmetry,2012,23,904-909.
[105] Zhensheng Ding. VANOL and VAPOL Chemistry: New Methodologies, LargeScale Synthesis, Derivatives, and Synthetic Applications[D].Michigan StateUniversity,2009.
[106] Hitoshi Ube, Satoko Fukuchi, Masahiro Terada. Enantioselective aza-Friedel–Crafts reaction catalyzed by a water inclusion complex of O,O’-diacyltartaric acid[J].Tetrahedron: Asymmetry,2010,21,1203–1205.
[107] Jonathan T. Reeves, Zhulin Tan, Zhengxu S. Han, Guisheng Li, Yongda Zhang,Yibo Xu,Diana C. Reeves, Nina C. Gonnella, Shengli Ma, Heewon Lee, BruceZ. Lu, Chris H. Senanayake. Direct Titanium-Mediated Conversion of Ketonesinto Enamides withAmmonia and Acetic Anhydride[J].Angew. Chem. Int. Ed.,2012,51,1400–1404.