Asymmetric Hydrocyanation of Alkenes without HCN

Li, Xiuxiu1,2; You, Cai1,2; Yang, Jiaxin3,4; Li, Shuailong3,4; Zhang, Dequan1,2; Lv, Hui3,4,5; Zhang, Xumu1,2,3,4

2019-07-09

10.1002/anie.201906111

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   影响因子和分区

1433-7851

1521-3773

A general and efficient rhodium-catalyzed asymmetric cyanide-free hydrocyanation of alkenes has been developed. Based on the asymmetric hydroformylation/condensation/aza-Cope elimination sequences, a broad scope of substrates including mono-substituted, 1,2-, and 1,1-disubstituted alkenes (involving natural product R- and S-limonene) were employed, and a series of valuable chiral nitriles are prepared with high yields (up to 95 %) and enantioselectivities (up to 98 % ee). Notably, the critical factor to achieve high enantioseletivies is the addition of catalytic amount of benzoic acid. This novel methodology provides an efficient and concise synthetic route to the intermediate of vildagliptin and anagliptin.

asymmetric synthesis hydrocyanation hydroformylation nitriles rhodium

SCI ; EI ; IC ; CCR

英语

NI期刊

第一 ; 通讯

Natural Science Foundation of Hubei Province[2018CFB430]

Chemistry

Chemistry, Multidisciplinary

WOS:000477471600001

WILEY-V C H VERLAG GMBH

20192807178257

Benzoic acid ; Cyanides ; Hydroformylation ; Rhodium

Precious Metals:547.1 ; Chemical Operations:802.3 ; Organic Compounds:804.1 ; Inorganic Compounds:804.2

CHEMISTRY

Web of Science

1.Southern Univ Sci & Technol, Grubbs Inst, Shenzhen 518000, Guangdong, Peoples R China
2.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518000, Guangdong, Peoples R China
3.Wuhan Univ, Key Lab Biomed Polymers, Minist Educ, Wuhan 430072, Hubei, Peoples R China
4.Wuhan Univ, Coll Chem & Mol Sci, Wuhan 430072, Hubei, Peoples R China
5.Wuhan Univ, Engn Res Ctr Organosilicon Cpds & Mat, Minist Educ, Coll Chem & Mol Sci,Sauvage Ctr Mol Sci, Wuhan 430072, Hubei, Peoples R China

Li, Xiuxiu,You, Cai,Yang, Jiaxin,et al. Asymmetric Hydrocyanation of Alkenes without HCN[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,2019,58(32):10928-10931.

Li, Xiuxiu.,You, Cai.,Yang, Jiaxin.,Li, Shuailong.,Zhang, Dequan.,...&Zhang, Xumu.(2019).Asymmetric Hydrocyanation of Alkenes without HCN.ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,58(32),10928-10931.

Li, Xiuxiu,et al."Asymmetric Hydrocyanation of Alkenes without HCN".ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 58.32(2019):10928-10931.