Rhodium-Catalyzed Chemo-, Regio- and Enantioselective Hydroformylation of Cyclopropyl-Functionalized Trisubstituted Alkenes

被引：11

作者：

Li, Shuailong ^{[1
,2
]}

Zhang, Dequan ^{[1
,2
]}

Zhang, Runtong ^{[1
,2
]}

Bai, Shao-Tao ^{[1
,2
,3
]}

Zhang, Xumu ^{[1
,2
,3
]}

机构：

[1] Southern Univ Sci & Technol, Dept Chem, 1088 Xueyuan Rd, Shenzhen 518055, Peoples R China

[2] Southern Univ Sci & Technol, Shenzhen Key Lab Small Mol Drug Discovery & Synth, 1088 Xueyuan Rd, Shenzhen 518055, Peoples R China

[3] Southern Univ Sci & Technol, Acad Adv Interdisciplinary Studies & Guangdong Pr, 1088 Xueyuan Rd, Shenzhen 518055, Peoples R China

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2022年 / 61卷 / 33期

基金：

中国国家自然科学基金;

关键词：

Enantioselective; Hydroformylation; Regioselective; Rhodium; Trisubstituted Alkenes; ANTI-MARKOVNIKOV HYDROFORMYLATION; ASYMMETRIC HYDROFORMYLATION; LIGANDS; OLEFINS; ESTERS; REARRANGEMENT; DERIVATIVES; REDUCTION; ALDEHYDES; DESIGN;

D O I：

10.1002/anie.202206577

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The first rhodium-catalyzed highly chemo-, regio- and enantioselective hydroformylation of cyclopropyl-functionalized trisubstituted alkenes affording useful chiral cyclopropyl entities is reported. Compared to generally used diphosphine ligands for asymmetric catalysis, the modified hybrid phosphorus ligand, named (R,S)-DTBM-Yanphos, can convert a series of readily available cyclopropyl-functionalized trisubstituted alkenes into high-value chiral cyclopropyl-functionalized aldehydes with high selectivities (81-98 % ee). Gram-scale reactions (TON up to 1500) and follow-up transformations to the corresponding alcohol, acid, esters and nitrile are also presented. Finally, a possible hydroformylation mechanism involving ring-open-hydroformylation pathways is proposed based on control and deuteroformylation reactions.

引用

页数：5

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