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From olefin cyclopropanation to olefin metathesis through catalyst engineering: recent applications of olefin metathesis to fine organic synthesis and to polymer chemistry
Author(s) -
Noels A. F.,
Demonceau A.
Publication year - 1998
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/(sici)1099-1395(199808/09)11:8/9<602::aid-poc50>3.0.co;2-u
Subject(s) - cyclopropanation , carbene , chemistry , metathesis , olefin fiber , ruthenium , catalysis , transition metal carbene complex , salt metathesis reaction , ring opening metathesis polymerisation , acyclic diene metathesis , combinatorial chemistry , organic chemistry , polymer chemistry , polymer , polymerization
An overview of the recent synthetic breakthroughs brought about by the discovery of new, functional group tolerant late transition metal (Rh and Ru)‐based catalysts is proposed. Whereas dirhodium(II)‐based complexes promote only carbene transfer reactions to olefins (i.e. olefin cyclopropanation), a few ruthenium‐based catalysts can be engineered and fine tuned so as to mediate either carbene‐transfer reactions or olefin metathesis. The different outcome of the reactions can be rationalized by the capability of the metal center to coordinate or not both the carbene and the olefin. This quite simple‐minded approach indicates that several available coordination sites at the metal center favors metathesis reactions to the prejudice of olefin cyclopropanation. Examples of recent applications in ring opening metathesis polymerizations and copolymerizations include the formation of postpolymers of polydienes, of carbohydrate‐substituted polymers and of telechelic oligomers. Application of the same ruthenium‐based catalysts in ring‐closing metathesis is illustrated by the formation of crown ether analogs, of unsaturated peptides and amino acids, of β‐lactams, and of different bicyclic systems.