A Boron Activating Effect Enables Cobalt-Catalyzed Asymmetric Hydrogenation of Sterically Hindered Alkenes

被引：60
作者：
Viereck, Peter [1 ]
Krautwald, Simon [1 ]
Pabst, Tyler P. [1 ]
Chirik, Paul J. [1 ]
机构：
[1] Princeton Univ, Dept Chem, Princeton, NJ 08544 USA
来源：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2020年 / 142卷 / 08期
基金：
瑞士国家科学基金会; 美国国家科学基金会;
关键词：
ENANTIOSELECTIVE HYDROGENATION; IRON; BORYLATION; OLEFINS; ESTERS; HYDROSILYLATION; HYDROBORATION; COMPLEXES; ALKYNES; SECONDARY;
D O I：
10.1021/jacs.9b12214
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
Unsymmetric 1,1-diboryl alkenes bearing one -[BPin] (BPin = pinacolatoboryl) and one -[BDan] (BDan = 1,8-diaminonaphthalatoboryl) substituent each were hydrogenated in high yield and enantioselectivity using C-1-symmetric pyridine(diimine) (PDI) cobalt complexes. High activities and stereoselectivities were observed with an array of 2-alkyl-, 2-aryl-, and 2-boryl-substituted 1,1-diboryl alkenes, giving rise to enantioenriched diborylalkane building blocks. Systematic study of substrate substituent effects identified competing steric and electronic demands in the key activating role of the boron substituents, whereby sterically unencumbered boronates such as -[BDan], -[BCat] (BCat = catecholatoboryl), and -[Beg] (Beg = ethylene glycolatoboryl) promote the hydrogenation of trisubstituted alkenes by enabling irreversible a-boron-directed insertion pathways to achieve otherwise challenging hydrogenations of trisubstituted alkenes. Deuterium-labeling studies with 1,1-diboryl alkenes support an insertion pathway generating a chiral intermediate with two different boron substituents and cobalt bound to the same carbon.
引用
收藏
页码：3923 / 3930
页数：8
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