锆、钛介导的烯烃、炔烃硼氢化

doi:10.6023/cjoc202212022

摘要/Abstract

过渡金属催化的烯烃、炔烃硼氢化反应是制备硼酸酯类化合物最为有效的方法之一, 该反应具有100%的原子经济性, 原料简单易得, 产物多样性可调等优点. 已知的金属催化剂大都依赖于铑、铱、钯、铂、钴、铁、铜等后过渡金属, 而使用前过渡金属锆、钛作为催化剂的反应体系则鲜有报道. 总结了锆、钛介导的(化学计量与催化量)烯烃、炔烃硼氢化反应的研究现状, 并对今后锆、钛催化的烯烃、炔烃硼氢化反应的发展进行了展望.

关键词: 锆, 钛, 烯烃, 炔烃, 硼氢化

The transition metal-catalyzed hydroboration of alkenes and alkynes is one of the most efficient way for the production of boronate esters. This type of reaction is 100% atom economic, the starting material is readily available, and the products are diverse. It is noticed that most of the known catalytic systems are based on late-transition-metals such as Rh, Ir, Pd, Pt, Co, Fe and Cu. The use of early-transition-metals of zirconium and titanium, on the other hand, is very scarce. In this short review, the development of application in zirconium and titanium mediated hydroboration of alkene and alkyne is summarized, and the research trends of this area are also discussed.

Key words: zirconium, titanium, alkenes, alkynes, hydroboration

引用此文

李思达, 舒兴中, 吴立朋. 锆、钛介导的烯烃、炔烃硼氢化[J]. 有机化学, 2023, 43(5): 1751-1760.

Sida Li, Xing-Zhong Shu, Lipeng Wu. Zirconium and Titanium Mediated Hydroboration of Alkenes and Alkynes[J]. Chinese Journal of Organic Chemistry, 2023, 43(5): 1751-1760.

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图/表 20

图式1. 有机硼化合物的转化、应用及烯烃、炔烃硼氢化反应

Scheme 1. Transformation and application of organoborons and hydroboration of alkenes and alkynes

图式2. 化学计量锆介导的烯基(烷基)硼合成

Scheme 2. Synthesis of alkenyl (alkyl) boron mediated by stoichiometric zirconium

图式3. Cp2ZrHCl催化炔烃硼氢化反应及可能机理

Scheme 3. Cp2ZrHCl-catalyzed hydroboration of alkynes and possible mechanism

图式4. Cp2ZrHCl催化末端炔烃硼氢化反应及可能机理

Scheme 4. Cp2ZrHCl-catalyzed hydroboration of terminal alkynes and possible mechanism

图式5. 锆/铜接力催化末端炔烃氢胺化反应

Scheme 5. Hydroamination of terminal alkynes via Zr/Cu relay catalysis

图式6. 末端炔烃一锅法合成环丙基硼酸酯

Scheme 6. One-pot synthesis of cyclopropylboronic esters from terminal alkynes

图式7. 锆催化合成烯基氨基硼烷

Scheme 7. Zirconium-catalyzed synthesis of alkenylaminoboranes

图式8. Cp2ZrHCl催化烯烃硼氢化反应

Scheme 8. Cp2ZrHCl-catalyzed hydroboration of alkenes

图式9. 锆催化烯烃脱氢硼化反应

Scheme 9. Dehydrogenative boration of alkenes enabled by zir- conium catalyst

图式10. 锆催化烯烃合成1,1-二硼烷烃

Scheme 10. Zirconium-catalyzed synthesis of 1,1-diborylalkanes from alkenes

图式11. 钛催化烯烃硼氢化反应

Scheme 11. Titanium-catalyzed alkenes hydroboration

图式12. 钛催化烯烃硼氢化反应及可能机理

Scheme 12. Titanium-catalyzed hydroboration of alkenes and possible mechanism

图式13. 钛催化烯烃癸烷硼烷硼氢化反应可能机理

Scheme 13. Possible mechanism for titanium-catalyzed decaborane-olefin hydroborations

图式14. 钛催化烯烃环硼化反应

Scheme 14. Titanium-catalyzed cycloboration of olefins

图式15. 钛介导的乙烯脱氢硼化反应

Scheme 15. Titanium-mediated dehydrogenative borylation of ethylene

图式16. 钛催化的乙烯脱氢硼化反应

Scheme 16. Titanium-catalyzed dehydrogenative borylation of ethylene

图式17. 钛催化的α-烯烃与二氯(二异丙胺)硼烷硼化反应及可能机理

Scheme 17. Titanium-catalyzed borylation of α-olefins with bis(diisopropylamino)chlorborane and possible mechanism

图式18. 钛催化的炔烃硼氢化反应

Scheme 18. Titanium-catalyzed hydroboration of alkynes

图式19. 钛催化的炔烃硼氢化反应可能机理

Scheme 19. Possible mechanism for titanium-catalyzed hydroboration of alkynes

图式20. 新型钛催化的末端炔烃硼氢化反应及可能机理

Scheme 20. Novel titanium-catalyzed hydroboration of terminal alkynes and possible mechanism

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