共轭双烯硼化质子化反应的研究进展

doi:10.6023/cjoc202105058

摘要/Abstract

共轭双烯的硼化质子化反应由于反应条件温和以及官能团兼容性广泛, 目前已经成为合成烯丙基硼化物以及高烯丙基硼化物的重要方法之一. 随着多个课题组在本领域取得重要进展, 共轭双烯的硼化质子化反应已经实现高化学选择性、区域选择性以及对映选择性转化. 此外一些基于硼化质子化的高效串联反应已被设计并实现, 并且有的方法已经被证实可以用于生物活性分子的高效合成. 近年来, 无过渡金属催化的共轭烯烃硼化质子化反应也被实现. 本综述将总结共轭双烯的硼化质子化反应的研究进展, 介绍各个反应的底物范围, 并讨论反应的机理过程.

关键词: 共轭双烯, 硼化质子化, 区域选择性, 对映选择性

The protoboration of conjugated diene is a kind of important strategy for the synthesis of allylic borides and homo-allylic borides, because of mild reaction conditions and wide functional group compatibility. Till now, several research groups have been reported key progress in this field, some of them could well control the chemical selectivity, regioselectivity and enantioselectivity of these transformations. In addition, some efficient tandem reactions which based on highly efficient protoboronation have been designed. These methods could be used for the synthesizing bioactive molecules via novel route. Furthermore, recently, the protoboronation of conjugated diene without transition metal catalyst has been realized. The research progress about protoboration of conjugated diene is summarized, the range of substrate scope is introduced, and the reaction mechanism for each reaction is discussed.

Key words: conjugated diene, protoboration, regioselectivity, enantioselectivity

引用此文

邹辰晨, 牛长浩, 刘新宇, 张淳. 共轭双烯硼化质子化反应的研究进展[J]. 有机化学, 2021, 41(11): 4240-4254.

Chenchen Zou, Changhao Niu, Xinyu Liu, Chun Zhang. Recent Advances about Protoboration of Conjugated Dienes[J]. Chinese Journal of Organic Chemistry, 2021, 41(11): 4240-4254.

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图/表 30

表1. Ito课题组报道的铜催化1,3-二烯的不对称硼化质子化反应

Table 1. Copper(I)-catalyzed asymmetric monoborylation of 1,3-dienes reported by Ito group

图式1. 铜催化1,3-二烯的不对称硼化质子化反应的反应机理

Scheme 1. Reaction mechanism of copper(i)-catalyzed asymmetric monoborylation of 1,3-dienes

表2. 铜催化的1,2-二氢吡啶的不对称硼化质子化反应

Table 2. Copper-catalyzed protoboration of 1,2-dihydropyridines

表3. 铜催化的1,2-二氢喹啉的不对称硼化质子化反应

Table 3. Copper-catalyzed asymmetric protoboronation of 1,2- dihydroquinolines

表4. 铜催化吡咯的硼化质子化及串联反应a,b

Table 4. Copper-catalyzed protoboration of pyrrole and tandem reaction

图式2. 铜催化的吡咯的硼化质子化的反应机理

Scheme 2. Possible reaction mechanism of copper-catalyzed protoboration of pyrrole

图式3. 非环状α,β,γ,δ-不饱和酮的1,6-硼化质子化反应

Scheme 3. 1,6-Protoboration of acyclic α,β,γ,δ-unsaturated ketones

表5. 铜催化树枝烯的硼化质子化反应

Table 5. Copper-catalyzed protoboration of borylated dendralenes

图式4. 铜催化树枝烯的硼化质子化反应的反应机理

Scheme 4. Possible reaction mechanism of copper-catalyzed protoboration of dendralenes

表6. 配体控制的铜催化化学、区域和对映选择性硼化质子化反应

Table 6. Ligand-controlled Cu-catalyzed chemo-, regio-, and enantio-selective protoboronation

表7. 非环状α,β,γ,δ-不饱和酮/酯的硼化质子化反应

Table 7. Protoboronation of acyclic α,β,γ,δ-unsaturated ketones/esters

表8. 环状α,β,γ,δ-不饱和酮的硼化质子化反应

Table 8. Protoboronation of cyclic α,β,γ,δ-unsaturated ketones

表9. 铜催化的共轭二烯硼酸盐硼化质子化反应

Table 9. Copper-catalyzed protoboronation of conjugated borate diene

图式5. 铜催化的共轭二烯硼酸盐的1,4-硼化质子化的反应机理

Scheme 5. Reaction mechanism of copper-catalyzed 1,4-protobornation of conjugated borate diene

表10. 铜催化立体选择性合成双硼产物

Table 10. Copper-catalyzed stereoselective synthesis of bisboron

表11. 铜催化对映选择性合成6元环硼酸的方法

Table 11. Copper-catalyzed enantioselective synthesis of 6- member-oxaboranoic acid

图式6. 铜催化对映选择性合成6元环硼酸的过渡态分析

Scheme 6. Transition state analysis about the formation of 6-member-oxaboranoic acid

表12. 硼化质子化及其产物的不对称转化研究

Table 12. Study of protoboronation and further asymmetric transformation

表13. 铜催化1,3-二烯的高选择性还原官能团化反应

Table 13. Copper-catalyzed highly selective reduction and functionalization of 1,3-diene

表14. 铜催化端1,3-二烯与二氧化碳的1,2-氢化羧基化反应

Table 14. Copper-catalyzed highly regioselective 1,2-hydrocarboxylation of 1,3-diene with carbon dioxide

图式7. 铜催化1,3-二烯与二氧化碳高度区域选择性1,2-氢化羧基化反应的机理

Scheme 7. Reaction mechanism of copper-catalyzed highly regioselective 1,2-hydrocarboxylation of 1,3-diene with carbon dioxide

表15. 铜和钯共催化末端1,3-二烯的高度区域选择性氢化芳基化反应

Table 15. Copper and palladium co-catalyzed the highly regioselective hydroarylation reaction of terminal 1,3-diene

图式8. 铜和钯共催化末端1,3-二烯的高度区域选择性氢化芳基化反应机理

Scheme 8. Reaction mechanism of Cu and Pd co-catalyzed highly regioselective hydroarylation of 1,3-diene

表16. 铜催化含三氟甲基的1,3-共轭二烯的硼化质子化反应

Table 16. Copper-catalyzed protoboration of CF3-containing 1,3- conjugated dienes

表17. 铜催化含三氟甲基的1,3-共轭二烯的对映选择性硼化质子化反应

Table 17. Copper-catalyzed enantioselective protoboration of CF3-containing 1,3-dienes

表18. 铜催化的1,3-共轭二烯高对映选择性的1,4-硼化质子化反应

Table 18. Copper-catalyzed highly enantioselective 1,4-protoboration of 1,3-dienes

表19. 铜催化2-取代1,3-二烯的硼化质子化研究

Table 19. Cu-catalyzed protoboronation of 2-substituted 1,3-dienes

表20. 铜催化α,β,γ,δ-不饱和羰基化合物对映选择性1,6-硼化质子化

Table 20. Copper-catalyzed enantioselective 1,6-protoboronation of α,β,γ,δ-unsaturated carbonyl compounds

表21. 反式-1-芳基-1,3-二烯的无过渡金属三硼化反应

Table 21. Transition-metal-free triboration of trans-1-aryl-1,3-dienes

表22. 无过渡金属的反式-1,3-二烯的1,4-氢化硼化反应

Table 22. Transition-metal-free 1,4-hydroboration of trans-1,3-dienes

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