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

Li，Shuailong1; Zhang，Dequan1; Zhang，Runtong1; Bai，Shao Tao1,2; Zhang，Xumu1,2

2022-07-01

10.1002/anie.202206577

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   影响因子和分区

1433-7851

1521-3773

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.

Enantioselective Hydroformylation Regioselective Rhodium Trisubstituted Alkenes

SCI ; EI

英语

NI论文

第一 ; 通讯

Guangdong Provincial Key Laboratory of Catalysis[2020B121201002] ; Shenzhen Key Laboratory of Small Molecule Drug Discovery and Synthesis[ZDSYS20190902093215877] ; Guangdong Basic and Applied Basic Research Foundation[2021A1515110808] ; National Natural Science Foundation of China[21991113]

Chemistry

Chemistry, Multidisciplinary

WOS:000822836500001

WILEY-V C H VERLAG GMBH

20222812344919

Catalysis ; Enantioselectivity ; Ligands ; Olefins

Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Chemical Operations:802.3 ; Organic Compounds:804.1

CHEMISTRY

Web of Science

1.Department of Chemistry and Shenzhen Key Laboratory of Small Molecule Drug Discovery and Synthesis,Southern University of Science and Technology,Shenzhen,1088 Xueyuan Road,518055,China
2.Academy for Advanced Interdisciplinary Studies and Guangdong Provincial Key Laboratory of Catalysis,Southern University of Science and Technology,Shenzhen,1088 Xueyuan Road,518055,China

Li，Shuailong,Zhang，Dequan,Zhang，Runtong,et al. Rhodium-Catalyzed Chemo-, Regio- and Enantioselective Hydroformylation of Cyclopropyl-Functionalized Trisubstituted Alkenes[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,2022,61.

Li，Shuailong,Zhang，Dequan,Zhang，Runtong,Bai，Shao Tao,&Zhang，Xumu.(2022).Rhodium-Catalyzed Chemo-, Regio- and Enantioselective Hydroformylation of Cyclopropyl-Functionalized Trisubstituted Alkenes.ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,61.

Li，Shuailong,et al."Rhodium-Catalyzed Chemo-, Regio- and Enantioselective Hydroformylation of Cyclopropyl-Functionalized Trisubstituted Alkenes".ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 61(2022).