Isothiourea-Catalysed Acylative Kinetic Resolution of Aryl-Alkenyl (sp2 vs. sp2) Substituted Secondary Alcohols

被引：24

作者：

Musolino, Stefania F. ^{[1
]}

Ojo, O. Stephen ^{[1
]}

Westwood, Nicholas J. ^{[1
]}

Taylor, James E. ^{[1
]}

Smith, Andrew D. ^{[1
]}

机构：

[1] Univ St Andrews, Sch Chem, EaStCHEM, St Andrews KY16 9ST, Fife, Scotland

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2016年 / 22卷 / 52期

基金：

英国工程与自然科学研究理事会;

关键词：

acylation; isothiourea; kinetic resolution; organocatalysis; renewable resources; ENANTIOSELECTIVE ACYL TRANSFER; ACHIRAL CARBOXYLIC-ACIDS; ALLYLIC ALCOHOLS; ASYMMETRIC ESTERIFICATION; PIVALIC ANHYDRIDE; SULFUR; HOMOBENZOTETRAMISOLE; BENZOTETRAMISOLE;

D O I：

10.1002/chem.201604788

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The non-enzymatic acylative kinetic resolution of challenging aryl-alkenyl (sp(2) vs. sp(2)) substituted secondary alcohols is described, with effective enantiodiscrimination achieved using the isothiourea organocatalyst HyperBTM (1 mol%) and isobutyric anhydride. The kinetic resolution of a wide range of aryl-alkenyl substituted alcohols has been evaluated, with either electron-rich or naphthyl aryl substituents in combination with an unsubstituted vinyl substituent providing the highest selectivity (S = 2-1980). The use of this protocol for the gram-scale (2.5 g) kinetic resolution of a model aryl-vinyl (sp(2) vs. sp(2)) substituted secondary alcohol is demonstrated, giving access to > 1 g of each of the product enantiomers both in 99:1 e.r.

引用

页码：18916 / 18922

页数：7

共 23 条

[21] The Construction of C-N, C-O, and C(sp2)-C(sp3) Bonds from Fluorine-Substituted 2-Aryl Benzazoles for Direct Synthesis of N-, O-, C-Functionalized 2-Aryl Benzazole Derivatives
Zhou, Quan
Hong, Xi
Cui, He-Zhen
Huang, Shuang
Yi, Ying
Hou, Xiu-Feng
JOURNAL OF ORGANIC CHEMISTRY, 2018, 83 (12): : 6363 - 6372
[22] Determination of the accurate values of the rate constant and thermodynamic parameters for the rotation about the C(sp2)-C(aryl) bond.: 3-substituted N,N,2,4,6-pentamethylbenzamides
Pribylová, E
Holík, M
COLLECTION OF CZECHOSLOVAK CHEMICAL COMMUNICATIONS, 1999, 64 (01) : 44 - 60
[23] Stereochemical Stability Differences between Axially Chiral 6-Aryl-Substituted Picolinic Esters and Their Benzoic Ester Derivatives: sp2N: vs. sp2CH in CH3, C6H5, and CH3O ortho-Substitution Effect
Tanaka, Shinji
Suzuki, Yusuke
Matsushita, Masaharu
Kitamura, Masato
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 2015, 88 (12) : 1726 - 1734

← 1 2 3 →