Tetrahedron p. 6117 - 6128 (1994)
Update date:2022-09-26
Topics:
Weber, Beat
Seebach, Dieter
In the presence of equimolar amounts of the Mg alkoxide from α,α,α',α'-tetraphenyl-2,2-dimethyl-1,3-dioxolan-4,5-dimethanol (a TADDOL) primary Grignard reagents (Et, Pr, Bu, Oct, 3-butenyl) add to carbo- and heteroaromatic methyl ketones in THF at -100°C to give tertiary alcohols of enantiomeric excesses reaching values above 98%. The scope and limitation of the method are investigated. The reaction, which occurs in a vigorously stirred heterogeneous mixture, give best results in the absence of steric hindrance of the reacting centers; Grignard reagents made from alkyl bromides are superior to those obtained from chlorides; there is a perfect linear relationship between the ee of the TADDOL and of the product 2-phenyl-2-decanol; those tertiary alcohols of which the absolute configuration is known, are formed by nucleophilic attack from the Re face of the keto carbonyl groups. Three tentative mechanistic models for the stereochemical course of the reaction are discussed.
View Morewebsite:http://www.guarson.com
Contact:+86-523-88059600,+86-13805268803
Address:Room B1006,Yafang Building,Jiangyan Avenue,Jiangyan District, Taizhou City,Jiangsu,China
Anhui Sholon New Material Technology Co., Ltd.
website:http://www.sholonchem.com
Contact:+86-550-5261666
Address:4/F Block B, Beijing Chemical Building.No.520 Tianrun Road ,Science & Education Town Wujin District, Changzhou City Jiangsu Province
Quhua Zhongxing Refrigeration Technology Co.,Ltd.
Contact:+86-5708886618
Address:318 Bulding 2, No.866 Quhua Rd.,Kecheng District
website:http://www.sigmaaldrich.com
Contact:800 558-9160
Address:Industriestrasse 25CH-9471 Buchs SGSwitzerland
Chengdu Biopurify Phytochemicals Ltd.
website:http://www.phytopurify.com
Contact:+86-28-82633397
Address:2F,No.11 Building,No.388 Rongtaidadao CNSTP,Wenjiang Zone,Chengdu,Sichuan, China
Doi:10.1021/jo00029a057
(1992)Doi:10.1002/chir.22016
(2012)Doi:10.1021/ol301130u
(2012)Doi:10.1002/adsc.201200944
(2013)Doi:10.1002/chem.201201757
(2012)Doi:10.1021/ja305403s
(2012)