铜催化硼试剂参与的烯烃多组分双官能化研究进展

doi:10.6023/cjoc202012010

摘要/Abstract

烯烃的多组分双官能化是一类高效快速构建结构多样性分子的重要有机反应, 具有原子经济性高、底物范围广及条件温和等诸多优点, 近年来成为有机合成领域的主要研究热点. 许多金属或非金属催化条件下的烯烃多组分双官能化反应已经被大量报道, 借助手性配体, 有的反应还成功地实现了不对称双官能化. 然而, 与贵重金属催化剂(钌、铑、铱、钯、银)相比, 价格低廉的过渡金属(铁、钴、镍、铜、锰)催化的有机反应更加受到人们的青睐. 考虑到铜催化剂和有机硼试剂在有机合成中的应用, 针对近三年来铜催化下有机硼试剂参与的烯烃多组分双官能化反应进行了综述, 并对该领域面临的挑战和发展方向进行了展望.

关键词: 铜催化, 硼试剂, 烯烃, 多组分双官能化

The multicomponent difunctionalization of alkenes is an important and highly efficient reaction for the rapid construction of molecules with structure diversity, which has some advantanges of high atom economy, wide substrate range as well as mild conditions and becomes the main research hotspot in organic synthesis in recent years. Many examples on the multicomponent difunctionalization of alkenes under metal-catalyzed or metal-free conditions have extentively been reported. Among them, the asymmetric version of some reactions was successfully achieved by the use of chiral ligands. However, compared with nobel metal catalysts such as ruthenium, rhodium, iridium, palladium and silver, the cheaper metal catalysts including iron, cobalt, nickel, copper, manganese have attracted more special attention. In view of the application of copper catalyst and organoboron reagents in organic synthesis, the advances in copper-catalyzed multicomponent difunctionalization of alkenes with organoboron reagents since 2018 are reviewed. The major challenges and development prospects of this fields, including the discovery of new reaction type and organoboron reagents, better stereoselectivity, and deeper understanding on reaction mechanism are also discussed.

Key words: copper-catalysis, boron reagent, alkene, multicomponent difunctionalization

引用此文

杨晨, 贾雪锋. 铜催化硼试剂参与的烯烃多组分双官能化研究进展[J]. 有机化学, 2021, 41(6): 2280-2289.

Chen Yang, Xuefeng Jia. Recent Advances in Copper-Catalyzed Boron-Reagent-Involved Multicomponent Difunctionalization of Alkenes[J]. Chinese Journal of Organic Chemistry, 2021, 41(6): 2280-2289.

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图/表 10

图式1. 铜催化硼试剂参与的烯烃多组分双官能化反应模式

Scheme 1. Reaction pattern on copper-catalyzed multicomponent difunctionalization of alkenes with organoboron reagents

图式2. 铜催化烷基烯烃的不对称硼氨基化反应

Scheme 2. Copper-catalyzed asymmetric aminoboration of alkyl-substituted alkenes

图式3. 催化剂控制的α-烷基烯基芳烃的1,1-和1,2-芳基硼化反应

Scheme 3. Catalyst-controlled 1,1- and 1,2-arylboration of α-alkyl alkenyl arenes

图式4. 铜和钯共催化烯基硼化合物的立体专一性芳基硼化反应

Scheme 4. Copper- and palladium-cocatalyzed stereospecific arylboration of alkenyl-Bdan compounds

图式5. 铜催化芳基烯烃的杂芳基硼化反应及可能的催化循环

Scheme 5. Copper-catalyzed borylative heteroarylation of vinylarenes and proposed catalytic cycle

图式6. 铜和钯协同催化芳烯的四组分硼羰基化反应

Scheme 6. Copper and palladium cooperative catalyzed four-component borocarbonylation of vinylarenes

图式7. 铜和钯协同催化芳烯的四组分硼羰基化反应机理

Scheme 7. Mechanism of copper and palladium cooperative catalyzed four-component borocarbonylation of vinylarenes

图式8. 铜催化脂肪烯烃的环丙烷化反应可能的机理

Scheme 8. Proposed mechanism of copper-catalyzed cyclopropanation of aliphatic alkenes

图式9. 铜催化试剂控制的芳基烯烃的区域选择性硼氰基化反应

Scheme 9. Copper-catalyzed reagent-controlled regioselective cyanoborylation of vinylarenes

图式10. 铜催化苯乙烯的自由基接力芳基磺酰化反应机理

Scheme 10. Mechanism of copper-catalyzed arylsulfonylation of styrenes via radical relay pathway

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