Nickel-catalyzed asymmetric grignard cross-coupling of dinaphthothiophene giving axially chiral 1,1'-binaphthyls

Toyoshi Shimada; Yong-Hwan Cho; Tamio Hayashi

doi:10.1021/ja0282588

Nickel-catalyzed asymmetric grignard cross-coupling of dinaphthothiophene giving axially chiral 1,1'-binaphthyls

J Am Chem Soc. 2002 Nov 13;124(45):13396-7. doi: 10.1021/ja0282588.

Authors

Toyoshi Shimada¹, Yong-Hwan Cho, Tamio Hayashi

Affiliation

¹ Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo, Japan.

PMID: 12418887
DOI: 10.1021/ja0282588

Abstract

Asymmetric cross-coupling of dinaphtho[2,1-b:1',2'-d]thiophene with ArMgBr (Ar = Ph, 4-MeC6H4, 4-MeOC6H4) proceeded with high enantioselectivity in THF at 20 degrees C in the presence of 3 mol % of a nickel catalyst generated from Ni(cod)2 and a chiral oxazoline-phosphine ligand to give high yields of axially chiral 2-mercapto-2'-aryl-1,1'-binaphthyls, whose enantiomeric excesses are over 93%. The mercapto group in the chiral binaphthyl was converted into iodo, boryl, and phosphino groups without racemization.