Catalytic Enantioselective Synthesis of Diarylmethanols from Aryl Bromides and Aldehydes by Using Organolithium Reagents

• Published in: European Journal of Organic Chemistry Vol. 2010; no. 34; pp. 6535 - 6538
• Main Authors: Nakagawa, Yuya, Muramatsu, Yusuke, Harada, Toshiro
• Format: Book Review Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01.12.2010; WILEY‐VCH Verlag; Wiley; Wiley-VCH
• Subjects: Alcohols; Aldehydes; Asymmetric catalysis; Chemistry; Chemistry, Organic; Condensed benzenic and aromatic compounds; Exact sciences and technology; Lithium; Noncondensed benzenic compounds; Organic chemistry; Physical Sciences; Preparations and properties; Science & Technology; Titanium; BORONIC ACIDS; KETONES; ALKYLATION; Titanium; Lithium; ASYMMETRIC ARYLATION; Aldehydes; Asymmetric catalysis; GRIGNARD-REAGENTS; Alcohols; Catalytic reaction; Chemical reagent; Enantioselectivity; Magnesium bromide; Aldehyde; Lithium Organic compounds; Phenols; Secondary alcohol; Chemical synthesis
• ISSN: 1434-193X; 1099-0690
• DOI: 10.1002/ejoc.201001254

A general method has been developed for preparing enantioenriched secondary alcohols by starting from aryl bromides and aldehydes. Aryl bromides were first treated with BuLi, and the resulting aryllithium reagents were mixed with titanium tetraisopropoxide and magnesium bromide. The reaction of aldehydes with the resulting mixed titanium reagents, in the presence of 3‐(3,5‐diphenylphenyl)‐H8‐BINOL (2 mol‐%) and titanium tetraisopropoxide, furnished the corresponding alcohols in high enantioselectivities and in high yields. The catalytic enantioselective arylation of aldehydes is realized by starting from readily available aryl bromides. Mixed titanium reagents, derived from aryllithium intermediates, titanium tetraisopropoxide, and magnesium bromide, underwent highly enantioselective addition to aldehydes in the presence of 2 mol‐% of DPP‐H8‐BINOL.