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Synthesis 2011(22): 3615-3626  
DOI: 10.1055/s-0031-1260251
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Aryl(chloro)methyl 4-Tolyl Sulfoxides: Synthesis and Application to the Synthesis of α-Aryl Ketones

Shigehiko Fukuda, Kazuhito Tsuji, Jun Musashi, Ryo Nonaka, Tsutomu Kimura, Tsuyoshi Satoh*
Graduate School of Chemical Sciences and Technology, Tokyo University of Science, Ichigaya-Funagawara-machi 12, Shinjuku-ku, Tokyo 162-0826, Japan
Fax: 81(3)52614631; e-Mail: tsatoh@rs.kagu.tus.ac.jp;
Further Information

Publication History

Received 21 July 2011
Publication Date:
05 October 2011 (online)

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Abstract

Aryl(chloro)methyl 4-tolyl sulfoxides were synthesized from arylmethyl 4-tolyl sulfoxides in moderate-to-good yields by sequential treatment with lithium diisopropylamide and tosyl chloride at low temperatures. Treatment of the lithium α-sulfinyl carbanion of the aryl(chloro)methyl 4-tolyl sulfoxides with aldehydes or ketones resulted in the formation of adducts in good-to-high yields. Treatment of these adducts with tert-butylmagnesium chloride gave the corresponding magnesium alkoxides. On treatment with isopropylmagnesium chloride, the alkoxides gave the corresponding magnesium β-oxido carbenoids, which rearranged to give α-aryl ketones in good-to-high yields. The magnesium enolate intermediates generated by rearrangement of the β-oxido carbenoids could also be trapped with electrophiles to give α-aryl α-substituted ketones. These procedures offer a good method for the synthesis of a variety of α-aryl ketones from aldehydes and ketones.

Key words

sulfoxides - α-aryl ketones - homologations - aldehydes

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