多取代烯烃的Z∶E高选择性合成制备

doi:10.6023/cjoc202212039

摘要/Abstract

烯烃是工业生产和药物合成中最常见的原料之一, 关于烯烃制备方法的报道层出不穷. 由于Z-构型烯烃与E-构型烯烃在理化性质和生物活性等方面存在很大的差异, 所以烯烃结构的Z∶E构型控制是合成方法学的热点之一. 综述了烯烃的立体选择性合成方法, 着重总结了双取代内烯烃和三取代烯烃的Z∶E构型的选择性制备. 以Z∶E选择性为主要分类标准, 解读了Wittig反应、取代烷烃消除反应、烯烃异构化反应、烯烃复分解反应、烯烃偶联反应、炔烃加成反应的相关报道, 并比较详细地描述了这些合成方法中的催化剂种类和Z∶E选择性的控制因素.

关键词: 双取代内烯烃, 三取代烯烃, Z∶E选择性

Olefin is one of the most important bulk chemicals in industry as well as commonly used starting materials in pharmaceutical field. Since Z-olefins and E-olefins exhibit great differences in physicochemical properties and biological activities, the Z∶E configuration control has been playing important roles in olefin preparation. The selective synthetic methods of Z∶E configurations of disubstituted inner alkenes and trisubstituted alkenes are reviewed, including the Wittig reaction, substituted alkane elimination reaction, olefin isomerization reaction, olefin metathesis, olefin coupling reaction, and alkyne addition reaction. The catalyst types and controlling factors of Z∶E selectivity in these synthetic examples are described in detail.

Key words: disubstituted internal olefins, trisubstituted olefins, Z∶E selectivity

引用此文

郭萍, 周勇, 赵杰. 多取代烯烃的Z∶E高选择性合成制备[J]. 有机化学, 2023, 43(3): 855-872.

Ping Guo, Yong Zhou, Jie Zhao. Z∶E Selective Preparation of Disubstituted Internal Alkenes and Trisubstituted Alkenes[J]. Chinese Journal of Organic Chemistry, 2023, 43(3): 855-872.

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图/表 64

图式1. 钌催化重氮化合物与硫叶立德的交叉烯烃反应

Scheme 1. Ruthenium-catalyzed cross-olefination of diazo compounds with sulfoxonium ylides Reproduced from Ref. [31] with permission from John Wiley and Sons

图式2. TrBF4催化的α-烷基重氮酯选择性生成Z-α,β-不饱和酯的反应和可能的机理

Scheme 2. Reaction and possible mechanism of selective formation of Z-α,β-unsaturated esters by α-alkyl diazo esters catalyzed by TrBF4 Reproduced from Ref. [32] with permission from the Royal Society of Chemistry

图式3. 光催化烯烃的构型转化

Scheme 3. Photocatalytic configuration transformation of olefin Reproduced from Ref. [33] with permission from the Royal Society of Chemistry

图式4. 二苯乙烯光氧化还原异构化催化剂在离子液体中的固定化研究

Scheme 4. Immobilization of the photoredox catalyst in ionic liquid for the photoredox isomerization of stilbene Reproduced from Ref. [34] with permission from John Wiley and Sons

图式5. 钌化合物催化的高Z-选择性和对映选择性开环/交叉复分解反应

Scheme 5. Ru complex catalyzed high Z-selectivity and enantioselectivity ring-open/cross metathesis reaction Reproduced from Ref. [37] with permission from the American Chemical Society

图式6. 钼化合物催化的烯烃复分解反应得到三氟甲基取代的烯烃

Scheme 6. Mo compound catalyzed olefin metathesis reactions to obtain trifluoromethyl-substituted olefin Reproduced from Ref. [39] with permission from Springer Nature

图式7. 钌催化的炔烃选择性半加氢反应

Scheme 7. Selective semi-hydrogenation of alkynes catalyzed by ruthenium Reproduced from Ref. [40] with permission from the American Chemical Society

图式8. 无负载纳米多孔钯催化剂催化炔烃半加氢反应机理

Scheme 8. Mechanism of semi-hydrogenation of alkynes catalyzed by an unsupported nanoporous palladium catalyst Reproduced from Ref. [41] with permission from the American Chemical Society

图式9. 异相钯催化炔烃选择性半氢化制备Z-烯烃

Scheme 9. Preparation of cis-alkenes by selective semi-hydro- genation of heterogeneous palladium-catalyzed alkynes Reproduced from Ref. [42] with permission from the American Chemical Society

图式10. 钯催化的配体调控炔烃的选择性氢化反应

Scheme 10. Palladium-catalyzed ligand regulating selective hydrogenation of alkynes Reproduced from Ref. [43] with permission from John Wiley and Sons

图式11. 钯催化的炔烃还原偶联反应

Scheme 11. Palladium-catalyzed alkyne reduction coupling reaction Reproduced from Ref. [44] with permission from John Wiley and Sons

图式12. 镍催化的炔烃选择性半氢化反应

Scheme 12. Nickel catalyzed selective semi-hydrogenation of alkynes Reproduced from Ref. [45] with permission from John Wiley and Sons

图式13. 铜催化的炔烃选择性氢烷基化反应

Scheme 13. Copper catalyzed selective hydroalkylation of alkynes Reproduced from Ref. [46] with permission from the American Chemical Society

图式14. 银催化的炔烃的氢烷基化反应可能的反应机理

Scheme 14. Possible mechanism of hydrogenalkylation of alkynes catalyzed by silver Reproduced from Ref. [48] with permission from the American Chemical Society

图式15. 苯乙酸直接脱羧消除制备烯烃

Scheme 15. Preparation of olefin by direct decarboxylation of phenylacetic acid Reproduced from Ref. [49] with permission from the American Chemical Society

图式16. 铁催化的甲基取代N-杂芳烃与伯醇发生α-烯化反应

Scheme 16. Fe-catalyzed α-olefination of methyl-substituted N-heteroarenes with primary alcohols Reproduced from Ref. [51] with permission from the American Chemical Society

图式17. 电子给体-受体反应脱羰基策略

Scheme 17. Decarbonylation strategies for electron donor-acce- ptor reactions Reproduced from Ref. [52] with permission from the Royal Society of Chemistry

图式18. 肼介导的镍催化酮的立体选择性烯化反应

Scheme 18. Nickel-catalyzed stereoselective alkenylation of ketones mediated by hydrazine Reproduced from Ref. [53] with permission from the American Chemical Society

图式19. 钴催化的β-取代苯乙烯Z-E异构化反应

Scheme 19. Cobalt-catalyzed Z to E isomerization of β-substi- tuted styrenes Reproduced from Ref. [54] with permission from the American Chemical Society