Abstract
Carbometallation in Organic Synthesis The addition of organometallic reagents to carbon-heteroatom unsaturated functional groups (C=O, C=N, CEN and C=S) has long been recognized as a versatile method for constructing carbon skeletons. Over one hundred years ago, in the l860’s, Butlerow and his school demonstrated the value of zinc alkyls for the synthesis of secondary and tertiary alcohols from carbonyl substrates [2]. Subsequent work by Grignard with magnesium reagents [3] and by Ziegler with lithium alkyls [4] established such carbometallations as indispensable synthetic reactions. The finding by Ziegler and coworkers in 1950’s that unsolvated aluminum alkyls add to unconjugated C=C and C=C linkages [5] not only broadened the scope of carbometallation, but also opened up new possibilities for stereochemical synthesis. Since Grignard reagents readily add to unconjugated carbon-carbon unsaturation only with anchimeric assistance [6–9] and since organolithium reagents often metallate and polymerize unsaturated hydrocarbons during attempted carbometallation [10], aluminum alkyls offer the synthetic chemist the complementary possibility of elaborating carbon skeletons from olefinic or acetylenic intermediates.
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Eisch, J.J., Manfre, R.J. (1979). Stereochemistry of the Carbometallation of Alkynylsilanes by Alkyl (Chloro)Bis-η5-Cyclopentadienyltitanium and the Initiation of Ethylene Polymerization by Homogeneous Ziegler-Natta Catalysts. In: Tsutsui, M. (eds) Fundamental Research in Homogeneous Catalysis. Springer, Boston, MA. https://doi.org/10.1007/978-1-4613-2958-9_26
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