Chiral Nonracemic Late-Transition-Metal Organometallics with a Metal-Bonded Stereogenic Carbon Atom: Development of New Tools for Asymmetric Organic Synthesis

✍ Scribed by Helena C. Malinakova

• Publisher: John Wiley and Sons
• Year: 2004
• Tongue: English
• Weight: 391 KB
• Volume: 10
• Category: Article
• ISSN: 0947-6539
• DOI: 10.1002/chem.200305667

✦ Synopsis

Abstract

Transition‐metal‐catalyzed cross‐coupling reactions and the Heck reaction have evolved into powerful tools for the construction of carbon–carbon bonds. In most cases, the reactive organometallic intermediates feature a carbon–transition‐metal σ bond between a sp^2^‐hybridized carbon atom and the transition metal (Csp^2^TM). New, and potentially more powerful approach to transition‐metal‐catalyzed asymmetric organic synthesis would arise if catalytic chiral nonracemic organometallic intermediates with a stereogenic sp^3^‐hybridized carbon atoms directly bonded to the transition metal (C*sp^3^TM bond) could be formed from racemic or achiral organic substrates, and subsequently participate in the formation of a new carbon–carbon bond (C*sp^3^–C) with retention of the stereochemical information. To date, only a few catalytic processes that are based on this concept, have been developed. In this account, both “classical” and recent studies on preparation and reactivity of stable chiral nonracemic organometallics with a metal‐bonded stereogenic carbon, which provide the foundation for the future design of new synthetic transformations exploiting the outlined concept, are discussed, along with examples of relevant catalytic processes.