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Synlett 2006(4): 0605-0609  
DOI: 10.1055/s-2006-932479
LETTER
© Georg Thieme Verlag Stuttgart · New York

Indium(I) Bromide Mediated Coupling of α,α-Dichloroketones with Carbonyl Compounds in Aqueous Media: The Preparation of 2-Chloro-3-hydroxy­propan-1-one Derivatives

Clovis Peppe*, Rafael Pavão das Chagas
Departamento de Química, Universidade Federal de Santa Maria-UFSM, Campus UFSM, Santa Maria, RS, 97105-900, Brazil
Fax: +55(55)32208031; e-Mail: peppe@quimica.ufsm.br;
Further Information

Publication History

Received 7 November 2005
Publication Date:
20 February 2006 (online)

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Abstract

Indium(I) bromide promotes the reductive coupling of α,α-dichloroketones with carbonyl compounds to the corresponding 2-chloro-3-hydroxypropan-1-one derivatives in moderate to good yields.

Key words

indium(I) bromide - dichloroketones - halogenomethyl indium(III) - 2-chloro-3-hydroxypropan-1-one - Darzens condensation

    References and Notes

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6

Crystallographic data for the compound C15H12BrClO2 (syn-2d) is deposited with the Cambridge Crystallographic Data Centre under the number CCDC 287226.

7

Crystallographic data for the compound C15H11BrO2 (trans-3d) is deposited with the Cambridge Crystallographic Data Centre under the number CCDC 287227.

8

α-Chloroacetophenone: 1H NMR (CDCl3): δ = 4.73 (s, 2 H), 7.51-7.97 (m, 5 H). 13C NMR (CDCl3): δ = 46.04, 128.46, 128.86, 133.99, 134.16, 191.03. MS (EI, 70 eV, for 35Cl): m/z (%) = 154 (10) [M], 105 (100), 77 (100), 51 (70).

14

Compounds 2a-q were isolated from column chromatography as a mixture of diastereomers. We notice that the NMR data correspond to the major fraction containing the mixtute isolated by column chromatography. Therefore, they do not correspond to the diastereomeric ratio described in Table [1] , which is the sum of all fractions containing the diastereomers.