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Chiral Nonracemic Late‐Transition‐Metal Organometallics with a Metal‐Bonded Stereogenic Carbon Atom: Development of New Tools for Asymmetric Organic Synthesis
Author(s) -
Malinakova Helena C.
Publication year - 2004
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200305667
Subject(s) - stereocenter , transition metal , catalysis , chemistry , carbon fibers , organic synthesis , enantioselective synthesis , organometallic chemistry , metal , combinatorial chemistry , organic chemistry , materials science , composite material , composite number
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.