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11
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33750084396
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For related reactions based on non-metal-catalyzed hydrostannation, see:
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N. J. A. Matrin B. List J. Am. Chem. Soc. 2006 128 13368
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Matrin, N.J.A.1
List, B.2
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14
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27544489337
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Trichlorosilane has been utilized for (asymmetric) 1,2-reduction of aldehydes, ketones, aldimines and ketimines in combination with (chiral) Lewis base-catalysts. For leading references, see:
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J. W. Yang M. T. H. Fonseca B. List J. Am. Chem. Soc. 2005 127 15036
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J. Am. Chem. Soc.
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Yang, J.W.1
Fonseca, M.T.H.2
List, B.3
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19
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33745661731
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A. V. Malkov A. J. P. Stewart Liddon P. Ramírez-López L. Bendová D. Haigh P. Kočovský Angew. Chem., Int. Ed. 2006 45 1432
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Malkov, A.V.1
Stewart Liddon, A.J.P.2
Ramírez-López, P.3
Bendová, L.4
Haigh, D.5
Kočovský, P.6
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20
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34447331272
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Cobalt(ii) chloride-catalyzed 1,4-reduction of enones or acryl esters with trichlorosilane has been reported, see:
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L. Zhou Z. Wang S. Wei J. Sun Chem. Commun. 2007 2977
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Chem. Commun.
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Zhou, L.1
Wang, Z.2
Wei, S.3
Sun, J.4
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21
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85047677817
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For a palladium-catalyzed reductive aldol reaction with trichlorosilane, see ref. 1c A patent that describes a formamide-catalyzed conjugate reduction of enones with the silane has been reported, see: Y. Matsumira and F. Iwasaki, Jpn. Pat., JP 2003171334 A. However, this patent does not describe the effect of Lewis bases other than formamides. Formamides are generally effective in the reduction of aldehydes with trichlorosilane, see ref. 4 For a pioneering study on aldol reaction of trichlorosilyl enolates, see:
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M. Chauhan P. Boudjouk Can. J. Chem. 2000 78 1396
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Can. J. Chem.
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Chauhan, M.1
Boudjouk, P.2
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23
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52649177906
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1H NMR study of the reaction of benzalacetone with trichlorosilane in deuterated dichloromethane confirmed the formation of the corresponding (Z)-trichlorosilyl enolate (assigned by a NOESY experiment), which supports a six-membered cyclic transition state with the s-cis conformation of enones (Figure). A similar mechanism has been suggested for borane reduction, see:
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1H NMR analysis of the crude reaction mixture using dibenzyl ether as an internal standard
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24
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0001595774
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Low diastereoselectivities (dr = 50: 50 to 78: 22) were observed in each case probably due to contributions of both catalyzed and non-catalyzed aldol processes, see ref. 7 We have employed BINAPO as a chiral Lewis base catalyst for enantioselective allylation, aldol reaction and epoxide ring-opening reaction, see:
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G. P. Boldrini M. Bortolotti F. Mancini E. Tagliavini C. Trombini A. Umani-Ronchi J. Org. Chem. 1991 56 5820
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Boldrini, G.P.1
Bortolotti, M.2
Mancini, F.3
Tagliavini, E.4
Trombini, C.5
Umani-Ronchi, A.6
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25
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33847632961
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The minor anti-isomer is racemic, which is consistent with the fact that the non-catalyzed aldol process favors the anti-product in a similar system, see ref. 7
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S. Kotani S. Hashimoto M. Nakajima Tetrahedron 2007 63 3122
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Tetrahedron
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Kotani, S.1
Hashimoto, S.2
Nakajima, M.3
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