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Synlett 2011(19): 2875-2879  
DOI: 10.1055/s-0031-1289854
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Catalytic Enantioselective Arylation of Aldehydes by Using Functionalized Grignard Reagents Generated from Aryl Bromides

Daisuke Itakura, Toshiro Harada*
Department of Chemistry and Materials Technology, Kyoto Institute of Technology, Matsugasaki, Sakyo-ku, Kyoto 606-8585, Japan
Fax: +81(75)7247514; e-Mail: harada@chem.kit.ac.jp;
Further Information

Publication History

Received 21 September 2011
Publication Date:
09 November 2011 (online)

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Abstract

An efficient catalytic method has been developed for the enantioselective synthesis of functionalized diarylmethanols starting from aryl bromides and aldehydes. In the presence of (R)-3-(3,5-diphenylphenyl)BINOL (2 mol%) and titanium tetraisopropoxide, functionalized aryl Grignard reagents (FGArMgCl; FG = 3-F3C, 4-F3C, 3-Br, 3-CN, 4-CN), prepared in situ by treatment of the bromides with i-PrMgCl˙LiCl, undergo addition to aldehydes to give the corresponding functionalized diarylmethanols in high enantioselectivities.

Key words

aldehydes - arylation - asymmetric catalysis - magnesium - titanium

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11

The mixed titanium reagent of 2-MeOC6H4MgBr and Ti(Oi-Pr)4 also underwent nonenantioselective reaction to an aldehyde.5c Intramolecular coordination of the ortho substituents to the titanium center might be responsible for the poor selectivities.