Enantioselective Friedel-Crafts
Alkylation of Furans and Indoles with Simple α,β-Unsaturated
Ketones Catalyzed by Oxazaborolidinone

Shinya Adachi; Fumi Tanaka; Kazuya Watanabe; Atsushi Watada; Toshiro Harada

doi:10.1055/s-0029-1218821

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Synthesis 2010(15): 2652-2669
DOI: 10.1055/s-0029-1218821

FEATUREARTICLE

Enantioselective Friedel-Crafts Alkylation of Furans and Indoles with Simple α,β-Unsaturated Ketones Catalyzed by Oxazaborolidinone

Shinya Adachi, Fumi Tanaka, Kazuya Watanabe, Atsushi Watada, Toshiro Harada*
Department of Chemistry and Materials Technology, Kyoto Institute of Technology, Matsugasaki, Sakyo-ku, Kyoto 606-8585, Japan
Fax: +81(75)7247580; e-Mail: harada@chem.kit.ac.jp;

Further Information

Publication History

Received 17 May 2010
Publication Date:
18 June 2010 (online)

Abstract
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Abstract

allo-Threonine-derived oxazaborolidinone (OXB) catalyzes the Friedel-Crafts alkylation of furans and indoles with simple acyclic α,β-unsaturated ketones to give the products in high yields and with high enantioselectivities. With 5-10 mol% of the OXB catalyst, enantioselectivities of up to 94% ee could be achieved for a variety of substrates. The use of N,N-dimethylaniline (2.5-10 mol%) as an additive is found to be essential for enantioselectivity. The effects of the additive are discussed in terms of the retardation of a proton-catalyzed racemic pathway, which deteriorates the enantioselectivity of the Friedel-Crafts reactions.

Key words

asymmetric catalysis - enones - Friedel-Crafts reaction - furans - indoles

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36

As 15f-d is more reactive than 15g, the deuterium contents of the products were influenced by the conversion of the reaction.

38

Alternatively, protonation of 23 at the enolate oxygen atom may afford the enol form of product 13 or 16, which undergoes tautomerization to the keto form with H/D scrambling. However, the effect of the amine additive is difficult to be rationalized by this pathway.