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

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

• 1 For discussion see: Peppe C. Curr. Org. Synth.  2004,  1:  227 
• 2 Peppe C. das Chagas RP. Synlett  2004,  1187 
• 3 Larger amounts of H₂O should be avoided because this induces disproportionation of the monobromide into indium metal and InBr₃. For discussion of disproportionation of indium monohalides in presence of donnor ligands, see: Peppe C. Tuck DG. Victoriano L. J. Chem. Soc., Dalton Trans.  1982,  2165 
• 4 Podlech J. Maier TC. Synthesis  2003,  633 
• 5 Arai S. Shirai Y. Ishida T. Shioiri T. Tetrahedron  1999,  55:  6375 
• 9 Bakó P. Czinege E. Bakó T. Czugler M. Tőke L. Tetrahedron: Asymmetry  1999,  10:  4539 
• 10a Concellón JM. Huerta M. Tetrahedron  2002,  58:  7775 
• 10b Concellón JM. Huerta M. Tetrahedron Lett.  2003,  44:  1931 
• 11 The authors also described the first successful aldol reaction between α,α-dichloroketones and aldehydes, catalyzed by samarium(III) hexamethyldisilazide, to produce 2,2-dichloro-3-hydroxypropan-1-one derivatives: Sasai H. Arai S. Shibasaki M. J. Org. Chem.  1994,  59:  2661 
• 12 Tanabe Y. Matsumoto N. Higashi T. Misaki T. Itoh T. Yamamoto M. Mitarai K. Nishii Y. Tetrahedron  2002,  58:  8269 
• 13 Araki S. Hirashita T. Shimizu K. Ikeda T. Butsugan Y. Tetrahedron  1996,  52:  2803 
• 15 Kitazume T. Jiang Z. Kasai K. Mihara Y. Suzuki M. J. Fluorine Chem.  2003,  121:  205 
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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.