含多氢键给体的双功能氨基—硫脲催化剂在不对称反应中的应用
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摘要
近年来，手性硫脲类催化剂因其独特的催化效果而备受有机化学家们的青睐。设计和合成了很多新型的、高效的手性硫脲类催化剂，其中手性氨基-硫脲是一类非常重要的有机小分子催化剂，已被成功地应用于Michael加成反应、Henry反应、Strecker反应、Baylis-Hillman反应、Diels-Alder等不对称催化反应中。我们课题组自主研发了含多氢键给体的手性双功能的氨基-硫脲类有机小分子催化剂，并将其应用于催化一些不对称反应，我的研究工作主要包括以下几个方面：
1.将一系列含多氢键给体的双功能氨基-硫脲类催化剂成功应用于硝基烷烃与N-叔丁酯亚胺类化合物的不对称Nitro-Mannich反应，其中NHSO2Ar的苯环上含有两拉电子的CF3的催化剂I-d表现出优异的催化活性。硝基甲烷与各种取代的芳香N-叔丁酯亚胺类化合物反应取得了85-99%的收率和96-99%ee的对映选择性；活性较差的、具有挑战性的烷基亚胺也取得了很好的结果，对映选择性高达98%ee。而且，其它硝基烷烃与各种芳基和烷基的N-叔丁酯亚胺类化合物的不对称Nitro-Mannich反应获得了较高的anti-选择性(93:7-99:1dr)和优异的对映选择性(96-99%ee)的含两个相邻手性中心的化合物。
2.催化剂I-d在催化硝基烃类化合物对芳基取代的-硝基烯烃类化合物的不对称Michael加成反应中也有不错的表现，一步构建了含两个相邻的手性中心的1,3-二硝基化合物，取得了优异的非对映选择性(高达98:2dr)和对映选择性(高达99%ee)，底物适用范围非常广。
3.运用催化剂I-d首次实现了-芳基环戊酮对-硝基烯烃类化合物的不对称Michael加成反应，底物适用范围广，得到了一系列优异的非对映选择性(>99:1dr)和对映选择性(90-96%ee)、含相邻的叔碳和季碳手性中心的产物。并且首次实现了-苯基环己酮对-硝基苯乙烯的加成反应，获得了中等的对映选择性(84%ee)。我们还对加成产物进行了一系列的转化，能方便地获得多官能团的环状亚胺、环状硝酮、四氢吡咯烷烃类等手性化合物。
4.催化剂I-d在各种硫酚、硫醇对4,4,4-三氟巴豆酸酯和4,4,4-三氟巴豆酰吡唑的不对称sulfa-Michael加成反应中表现出优异的催化活性，底物适用范围非常广，构建了一系列高立体选择性的手性中心碳原子同时含有硫原子和三氟甲基的化合物。两个反应催化体系所得到的sulfa-Michael加成的产物的构型相反，能够方便地获得两种构型的产物。加成产物在酸性条件下被水解得到的羧酸类化合物是基质金属蛋白酶MMP-3的高效抑制剂即γ-trifluoromethyl γ-sulfone hydroxamate的重要中间体。
In recent years, much attention was paid to chiral thiourea catalysts owing to their uniquecatalytic effects. Many novel and effective chiral thiourea catalysts were designed andsynthesized, chiral amine-thiourea was one of the most important organocatalysts. It wassuccessfully applied into a lot of asymmetric reactions, such as Michael addition, Henryreaction, Strecker reaction, Baylis-Hillman reaction, Diels-Alder reaction. Chiral bifunctionalamine-thiourea catalysts bearing multiple hydrogen bonding donors were independentlydeveloped by our group, and they were made application into many asymmetric reactions, myresearch contents were as followed:
1. A series of chiral bifunctional amine-thiourea catalysts bearing multiple hydrogenbonding donors were successfully applied into asymmetric nitro-Mannich reactions, thecatalyst I-d bearing two electron-withdrawing CF3groups on the aromatic ring ofsulfonamide NHSO2Ar emerged as the most effective catalyst. A variety of aryl N-Bocaldimines reacted with nitromethane smoothly to afford the corresponding products in highyields (85-99%) and excellent enantioselectivities (96-99%ee). Moreover, the poor reactiveand challenging alkyl N-Boc aldimines also obtained good results, the enantioselectivity wasup to98%ee. Indeed, other nitroalkanes and various N-Boc aldimines have proven to beexcellent substrates with respect to diastereo-/enantioselectivity and reactivity, thecorresponding products with two contiguous stereogenic centers were obtained in high yieldsand excellent diastereo-/enantioselectivities (93:7-99:1dr,96-99%ee).
2. A highly diastereoselective and enantioselective Michael addition of nitroalkanes tonitroolefns has been achieved by chiral bifunctional amine-thiourea catalyst I-d. Thiscatalytic system proceeded well over a broad scope of substrates, furnishing various1,3-dinitro compounds in high diastereoselectivities (up to98:2dr) and excellentenantioselectivities (up to99%ee).
3. We have developed the frst asymmetric Michael addition of-aryl cyclopentanonesand nitroolefns catalyzed by bifunctional amine-thiourea catalyst I-d. This catalytic systemperformed well over a broad scope of substrates and provided a series of the desired adductscontaining adjacent quaternary and tertiary stereogenic centers with excellentdiastereoselectivities (>99:1dr) and high enantioselectivities (90-96%ee), and it also realizedthe asymmetric Michael addition of-phenyl cyclohexanone and nitroolefn for the first time.The subsequent transformations led to expedient preparation of synthetically useful cyclicimine, nitrone and fused pyrrolidine.
4. We first successfully developed the highly efficient asymmetric sulfa-Michael addition of thiols to ethyl4,4,4-trifluorocrotonate and4,4,4-trifluorocrotonamide catalyzed bybifunctional amine-thiourea catalyst I-d. They can be served as general methods for the directconstruction of chiral building blocks bearing a unique trifluoromethyl group and a sulfuratom at the stereogenic carbon center. And different configurational products can be easilyobtained through these sulfa-Michael additions. The products were efficiently hydrolyzed togive the key intermediate in the preparation of the potent inhibitor of MMP-3(stromelysin-1),-trifluoromethyl-sulfone hydroxamate.
1.将一系列含多氢键给体的双功能氨基-硫脲类催化剂成功应用于硝基烷烃与N-叔丁酯亚胺类化合物的不对称Nitro-Mannich反应，其中NHSO2Ar的苯环上含有两拉电子的CF3的催化剂I-d表现出优异的催化活性。硝基甲烷与各种取代的芳香N-叔丁酯亚胺类化合物反应取得了85-99%的收率和96-99%ee的对映选择性；活性较差的、具有挑战性的烷基亚胺也取得了很好的结果，对映选择性高达98%ee。而且，其它硝基烷烃与各种芳基和烷基的N-叔丁酯亚胺类化合物的不对称Nitro-Mannich反应获得了较高的anti-选择性(93:7-99:1dr)和优异的对映选择性(96-99%ee)的含两个相邻手性中心的化合物。
2.催化剂I-d在催化硝基烃类化合物对芳基取代的-硝基烯烃类化合物的不对称Michael加成反应中也有不错的表现，一步构建了含两个相邻的手性中心的1,3-二硝基化合物，取得了优异的非对映选择性(高达98:2dr)和对映选择性(高达99%ee)，底物适用范围非常广。
3.运用催化剂I-d首次实现了-芳基环戊酮对-硝基烯烃类化合物的不对称Michael加成反应，底物适用范围广，得到了一系列优异的非对映选择性(>99:1dr)和对映选择性(90-96%ee)、含相邻的叔碳和季碳手性中心的产物。并且首次实现了-苯基环己酮对-硝基苯乙烯的加成反应，获得了中等的对映选择性(84%ee)。我们还对加成产物进行了一系列的转化，能方便地获得多官能团的环状亚胺、环状硝酮、四氢吡咯烷烃类等手性化合物。
4.催化剂I-d在各种硫酚、硫醇对4,4,4-三氟巴豆酸酯和4,4,4-三氟巴豆酰吡唑的不对称sulfa-Michael加成反应中表现出优异的催化活性，底物适用范围非常广，构建了一系列高立体选择性的手性中心碳原子同时含有硫原子和三氟甲基的化合物。两个反应催化体系所得到的sulfa-Michael加成的产物的构型相反，能够方便地获得两种构型的产物。加成产物在酸性条件下被水解得到的羧酸类化合物是基质金属蛋白酶MMP-3的高效抑制剂即γ-trifluoromethyl γ-sulfone hydroxamate的重要中间体。
In recent years, much attention was paid to chiral thiourea catalysts owing to their uniquecatalytic effects. Many novel and effective chiral thiourea catalysts were designed andsynthesized, chiral amine-thiourea was one of the most important organocatalysts. It wassuccessfully applied into a lot of asymmetric reactions, such as Michael addition, Henryreaction, Strecker reaction, Baylis-Hillman reaction, Diels-Alder reaction. Chiral bifunctionalamine-thiourea catalysts bearing multiple hydrogen bonding donors were independentlydeveloped by our group, and they were made application into many asymmetric reactions, myresearch contents were as followed:
1. A series of chiral bifunctional amine-thiourea catalysts bearing multiple hydrogenbonding donors were successfully applied into asymmetric nitro-Mannich reactions, thecatalyst I-d bearing two electron-withdrawing CF3groups on the aromatic ring ofsulfonamide NHSO2Ar emerged as the most effective catalyst. A variety of aryl N-Bocaldimines reacted with nitromethane smoothly to afford the corresponding products in highyields (85-99%) and excellent enantioselectivities (96-99%ee). Moreover, the poor reactiveand challenging alkyl N-Boc aldimines also obtained good results, the enantioselectivity wasup to98%ee. Indeed, other nitroalkanes and various N-Boc aldimines have proven to beexcellent substrates with respect to diastereo-/enantioselectivity and reactivity, thecorresponding products with two contiguous stereogenic centers were obtained in high yieldsand excellent diastereo-/enantioselectivities (93:7-99:1dr,96-99%ee).
2. A highly diastereoselective and enantioselective Michael addition of nitroalkanes tonitroolefns has been achieved by chiral bifunctional amine-thiourea catalyst I-d. Thiscatalytic system proceeded well over a broad scope of substrates, furnishing various1,3-dinitro compounds in high diastereoselectivities (up to98:2dr) and excellentenantioselectivities (up to99%ee).
3. We have developed the frst asymmetric Michael addition of-aryl cyclopentanonesand nitroolefns catalyzed by bifunctional amine-thiourea catalyst I-d. This catalytic systemperformed well over a broad scope of substrates and provided a series of the desired adductscontaining adjacent quaternary and tertiary stereogenic centers with excellentdiastereoselectivities (>99:1dr) and high enantioselectivities (90-96%ee), and it also realizedthe asymmetric Michael addition of-phenyl cyclohexanone and nitroolefn for the first time.The subsequent transformations led to expedient preparation of synthetically useful cyclicimine, nitrone and fused pyrrolidine.
4. We first successfully developed the highly efficient asymmetric sulfa-Michael addition of thiols to ethyl4,4,4-trifluorocrotonate and4,4,4-trifluorocrotonamide catalyzed bybifunctional amine-thiourea catalyst I-d. They can be served as general methods for the directconstruction of chiral building blocks bearing a unique trifluoromethyl group and a sulfuratom at the stereogenic carbon center. And different configurational products can be easilyobtained through these sulfa-Michael additions. The products were efficiently hydrolyzed togive the key intermediate in the preparation of the potent inhibitor of MMP-3(stromelysin-1),-trifluoromethyl-sulfone hydroxamate.
引文
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