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.

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 

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).

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 

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.

15 Kitazume T. Jiang Z. Kasai K. Mihara Y. Suzuki M. J. Fluorine Chem.  2003,  121:  205 

16 Kumaraswamy G. Sastry MNV. Jena N. Kumar KR. Vairamani M. Tetrahedron: Asymmetry  2003,  14:  3797