- The Kharasch reaction revisited: CuX3Li2-catalyzed conjugate addition reactions of Grignard reagents
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The conjugate addition of Grignard reagents RMgX to α,β-unsaturated ketones and esters is effectively catalyzed by soluble copper ate-complexes of the type CuX3Li2, e.g.CuI*2LiCl.In the presence of Me3SiCl the corresponding ketone enolsilanes are formed in high yield and selectivity.Diastereoselectivity in the case of chiral ketones is similar to that observed by using stoichiometric amounts of cuprates R2CuLi.Thus CuX3Li2-catalyzed 1,4-additions of Grignard reagents may be an industrially viable process.Keywords: Copper; Magnesium; Lithium; Silicon; Ketone; Enolsilanes
- Reetz, Manfred T.,Kindler, Alois
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- CHLOROSILANE-ACCELERATED CONJUGATE ADDITION OF CATALYTIC AND STOICHIOMETRIC ORGANOCOPPER REAGENTS
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Trialkylsilyl chlorides, particularly in combination with hexamethylphosphoramide or 4-dimethylaminopyridine, dramatically accelerates the conjugate addition of catalytic and stoichiometric organocopper reagents onto enones, enals, and enoates, in which very high degrees of stereo- and chemoselectivities were observed.
- Matsuzawa, Satoshi,Horiguchi, Yoshiaki,Nakamura, Eiichi,Kuwajima, Isao
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p. 349 - 362
(2007/10/02)
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- Me3SiCl ACCELERATED CONJUGATE ADDITION OF STOICHIOMETRIC ORGANOCOPPER REAGENTS
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Chlorotrimethylsilane, particularly if combined with hexamethylphosphoric triamide or 4-dimethylaminopyridine, strongly promote the conjugate addition of stoichiometric organocopper reagents.
- Nakamura, Eiichi,Matsuzawa, Satoshi,Horiguchi, Yoshiaki,Kuwajima, Isao
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p. 4029 - 4032
(2007/10/02)
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- HIGHLY SELECTIVE, KINETICALLY CONTROLLED ENOLATE FORMATION USING LITHIUM DIALKYLAMIDES IN THE PRESENCE OF TRIMETHYLCHLOROSILANE
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The deprotonation of ketones and esters with lithium dialkylamides in the presence of trimethylchlorosilane leads to enhanced selectivity for the kinetically generated enolate.Lithium t-octyl-t-butylamide is shown to be superior to lithium diisopropylamid
- Corey, E. J.,Gross, Andrew W.
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p. 495 - 498
(2007/10/02)
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