钯催化Suzuki-Miyaura交叉偶联反应和分子内Heck反应的研究
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摘要
本论文主要研究了醋酸钯/β-羰基胺催化体系催化Suzuki-Miyaura交叉偶联反应,N-芳基炔酰胺的亲电自位环化反应以及1-(2-碘苄基)-螺[4.5]三烯-8-酮的分子内Heck反应。Suzuki-Miyaura交叉偶联反应、亲电自位环化反应和Heck反应都是有机合成中构建新的C-C键的重要方法。论文主要研究内容如下:
(1)对钯催化Suzuki-Miyaura交叉偶联反应和Heck反应的近几年的研究进展作了综述。主要从配体、催化剂、助催化剂和机理等四个方面详细地对Suzuki-Miyaura交叉偶联反应和Heck反应的进展进行了介绍和讨论。
(2)发展了醋酸钯/β-羰基胺催化体系高效催化卤代芳烃与芳基硼酸的Suzuki-Miyaura交叉偶联反应。在醋酸钯和N-(4-甲氧基苯基)-3-羰基丁酰胺作用下,卤代芳烃与芳基硼酸能够在温和的条件下发生偶联反应,以高的产率得到相应的偶联产物,催化效率也很高(TONs=950 000,TOFs=79 167)。实验证明,N-(4-甲氧基苯基)-3-羰基丁酰胺是一种价廉且高效的配体。
(3)研究了芳基炔酰胺在NBS亲电试剂的作用下,发生亲电自位环化反应。我们发现N-邻碘苄基-芳基炔酰胺在NBS的亲电试剂作用下,通过分子内亲电自位环化反应,生成了螺[4,5]三烯-8-酮类化合物。
(4)研究了1-(2-碘苄基)-螺[4,5]三烯-8-酮在两种不同催化体系中的Heck反应:(1)在醋酸钯、三苯基膦和NaHCO_3的作用下、温度为120℃的氩气氛中迅速反应,反应物中的碘原子进攻螺环上6-位碳原子,在分子内部形成一种带六元环结构的新物质;(2)在PdCl_2(Ph_3P)_2、TBAB和Et_3N的作用下,温度为120℃的氩气氛中反应12小时,反应物中的碘原子进攻螺环上6-位碳原子,同时螺环上的6-位双键被还原成单键,在分子内部形成另一种带六元环的新物质。
The contents of this thesis include(ⅰ) the Pd(OAc)_2/β-Oxo amides catalyze Suzuki-Miyaura cross-coupling reaction,(ⅱ) ipso-cyclizations of 1-(2-iodobenzyl)-1-azaspiro[4.5]-triene-8-ones,and(ⅲ) the Heck reactions of 1-(2-iodobenzyl)-1-azaspiro[4.5]-triene-8-ones.The Suzuki-Miyaura reaction,ipso-cyclization reaction and Heck reaction are the important methods for the construction of new C-C bonds in organic synthesis.
1.Progress in the palladium-catalyzed Suzuki-Miyaura cross-coupling reaction and Heck reaction are summarized.We discussed the effects of ligands,catalysts,and additives on the Suzuki-Miyaura cross-coupling reaction and Heck reaction detailedly.The mechanisms are also reviewed.
2.The Suzuki-Miyaura cross-coupling reaction of aryl halides and arylboronic acids has been developed using Pd(OAc)_2/β-Oxo amides as the catalytic system.In the presence of Pd(OAc)_2 and N-(4-methoxyphenyl)-3-oxobutanamide,a variety of aryl halides were coupled with arylboronic acids successfully in moderate to excellent yields provding high turnover numbers(maximum TONs=950 000 and TOFs= 79 167).The results showed that N-(4-methoxyphenyl)-3-oxobutanamide was an inexpensive and efficient ligand.
3.ipso-Cyclization of N-arylpropiolamides was studied in the presence of NBS.We found that N-(2-iodobenzyl)-N-aryl-3-phenyl propiolamides could undergo the intramolecular electrophilic ipsocyclization with NBS to synthesize the corresponding spiro[4,5]trine-8-ones in good yields.
4.Two catalytic systems for the Heck reactions of 1-(2-iodobenzyl) -1-azaspiro[4.5]-triene-8-ones have been developed:(1) Pd(OAc)_2 combined with PPh_3 and NaHCO_3 was found to be an efficient catalytic system for the Heck reactions of 1-(2-iodobenzyl)-1-azaspiro[4.5]-triene-8-ones at 120℃under the argon atmosphere.1-(2-Iodobenzyl)-1-azaspiro[4,5]-triene-8-ones underwent the intramoleecular Heck reaction with this catalytic system smoothly to construct a new six-membered ring. (2) Another efficient catalytic system has also been developed,in the presence of PdCl_2(PPh3)2/TBAB/Et_3N,the Heck reactions of 1-(2-iodobenzyl)-1-azaspiro[4.5]-triene-8-ones were conducted successfully at 120℃under the atmosphere of argon,followed by protonation to afford the crossponding six-membered-ring products.
(1)对钯催化Suzuki-Miyaura交叉偶联反应和Heck反应的近几年的研究进展作了综述。主要从配体、催化剂、助催化剂和机理等四个方面详细地对Suzuki-Miyaura交叉偶联反应和Heck反应的进展进行了介绍和讨论。
(2)发展了醋酸钯/β-羰基胺催化体系高效催化卤代芳烃与芳基硼酸的Suzuki-Miyaura交叉偶联反应。在醋酸钯和N-(4-甲氧基苯基)-3-羰基丁酰胺作用下,卤代芳烃与芳基硼酸能够在温和的条件下发生偶联反应,以高的产率得到相应的偶联产物,催化效率也很高(TONs=950 000,TOFs=79 167)。实验证明,N-(4-甲氧基苯基)-3-羰基丁酰胺是一种价廉且高效的配体。
(3)研究了芳基炔酰胺在NBS亲电试剂的作用下,发生亲电自位环化反应。我们发现N-邻碘苄基-芳基炔酰胺在NBS的亲电试剂作用下,通过分子内亲电自位环化反应,生成了螺[4,5]三烯-8-酮类化合物。
(4)研究了1-(2-碘苄基)-螺[4,5]三烯-8-酮在两种不同催化体系中的Heck反应:(1)在醋酸钯、三苯基膦和NaHCO_3的作用下、温度为120℃的氩气氛中迅速反应,反应物中的碘原子进攻螺环上6-位碳原子,在分子内部形成一种带六元环结构的新物质;(2)在PdCl_2(Ph_3P)_2、TBAB和Et_3N的作用下,温度为120℃的氩气氛中反应12小时,反应物中的碘原子进攻螺环上6-位碳原子,同时螺环上的6-位双键被还原成单键,在分子内部形成另一种带六元环的新物质。
The contents of this thesis include(ⅰ) the Pd(OAc)_2/β-Oxo amides catalyze Suzuki-Miyaura cross-coupling reaction,(ⅱ) ipso-cyclizations of 1-(2-iodobenzyl)-1-azaspiro[4.5]-triene-8-ones,and(ⅲ) the Heck reactions of 1-(2-iodobenzyl)-1-azaspiro[4.5]-triene-8-ones.The Suzuki-Miyaura reaction,ipso-cyclization reaction and Heck reaction are the important methods for the construction of new C-C bonds in organic synthesis.
1.Progress in the palladium-catalyzed Suzuki-Miyaura cross-coupling reaction and Heck reaction are summarized.We discussed the effects of ligands,catalysts,and additives on the Suzuki-Miyaura cross-coupling reaction and Heck reaction detailedly.The mechanisms are also reviewed.
2.The Suzuki-Miyaura cross-coupling reaction of aryl halides and arylboronic acids has been developed using Pd(OAc)_2/β-Oxo amides as the catalytic system.In the presence of Pd(OAc)_2 and N-(4-methoxyphenyl)-3-oxobutanamide,a variety of aryl halides were coupled with arylboronic acids successfully in moderate to excellent yields provding high turnover numbers(maximum TONs=950 000 and TOFs= 79 167).The results showed that N-(4-methoxyphenyl)-3-oxobutanamide was an inexpensive and efficient ligand.
3.ipso-Cyclization of N-arylpropiolamides was studied in the presence of NBS.We found that N-(2-iodobenzyl)-N-aryl-3-phenyl propiolamides could undergo the intramolecular electrophilic ipsocyclization with NBS to synthesize the corresponding spiro[4,5]trine-8-ones in good yields.
4.Two catalytic systems for the Heck reactions of 1-(2-iodobenzyl) -1-azaspiro[4.5]-triene-8-ones have been developed:(1) Pd(OAc)_2 combined with PPh_3 and NaHCO_3 was found to be an efficient catalytic system for the Heck reactions of 1-(2-iodobenzyl)-1-azaspiro[4.5]-triene-8-ones at 120℃under the argon atmosphere.1-(2-Iodobenzyl)-1-azaspiro[4,5]-triene-8-ones underwent the intramoleecular Heck reaction with this catalytic system smoothly to construct a new six-membered ring. (2) Another efficient catalytic system has also been developed,in the presence of PdCl_2(PPh3)2/TBAB/Et_3N,the Heck reactions of 1-(2-iodobenzyl)-1-azaspiro[4.5]-triene-8-ones were conducted successfully at 120℃under the atmosphere of argon,followed by protonation to afford the crossponding six-membered-ring products.
引文
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