Asymmetric NaBH4 1,4-Reduction of C3-Disubstituted 2-Propenoates Catalyzed by a Diamidine Cobalt Complex

被引：16

作者：

Shuto, Yoshihiro ^{[1
,2
]}

Yamamura, Tomoya ^{[1
,2
]}

Tanaka, Shinji ^{[1
,2
]}

Yoshimura, Masahiro ^{[3
]}

Kitamura, Masato ^{[1
,2
]}

机构：

[1] Nagoya Univ, Grad Sch Sci, Grad Sch Pharmaceut Sci, Chikusa Ku, Nagoya, Aichi 4648601, Japan

[2] Nagoya Univ, Res Ctr Mat Sci, Chikusa Ku, Nagoya, Aichi 4648601, Japan

[3] Aichi Gakuin Univ, Div Liberal Arts & Sci, Iwasaki, Nisshin 4700195, Japan

来源：

CHEMCATCHEM | 2015年 / 7卷 / 10期

基金：

日本科学技术振兴机构;

关键词：

asymmetric catalysis; carboxylic esters; cobalt; reduction; sodium borohydride; CONJUGATE REDUCTION; ACID-DERIVATIVES; STRUCTURAL-CHARACTERIZATION; HYDROGENATION; LIGAND; ESTERS; BOROHYDRIDE; SEMICORRIN; CHEMISTRY; BOND;

D O I：

10.1002/cctc.201500260

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

A new Co complex of a unique diamidine ligand catalyzes asymmetric NaBH4 reduction of C3-disubstituted (E)- and (Z)-2-propenoates, including C3-oxygen- and nitrogen-substituted substrates with high enantioselectivity. Analysis by X-ray diffraction, (HNMR)-H-1 spectroscopy, ring-opening radical-clock and D-labeling reactions, and the structure/selectivity relationship suggest that a mechanism of CoH-involved non-single-electron transfer 1,4-addition differentiates the C2 enantioface. Involvement of CoH species has been supported by quantitative isolation of a new type of CoH2(BH3)(2) complex.

引用

页码：1547 / 1550

页数：4

共 37 条

[1] Asymmetric homogeneous hydrogenations at scale [J].