Journal of Organometallic Chemistry p. 57 - 76 (1987)
Update date:2022-08-04
Topics:
Doetz, Karl Heinz
Popall, Michael
Mueller, Gerhard
Carbonylcarbene complexes bearing either heteroatoms or C=C bonds in a carbene γ-position are susceptible towards facile decarbonylation.The coordination of the additional donor group affords stable five-membered metal carbene chelates.Olefin-chelated metallacycles are obtained via aminolysis of alkoxy carbene complexes using allylamine.Heteroatom metal carbene chelates are accessible from ortho-lithiated methoxyarenes in a two-step process involving a sequential nucleophile/electrophile addition to metal carbonyls followed by thermal decarbonylation.Both types of compounds have been studied systematically by X-ray analysis.The characteristic feature of oxametallacycles is a long metal to oxygen bond.The ready ring-opening is exploited in the carbene annulation reaction in which now the ligand coupling can be separated from the generation of a vacant coordination site at the metal template.The scope of this strategy is demonstrated by two approaches to anthracyclinones: Either ring B or ring C can be formed from 1,4-dimethoxy-2-naphtylcarbene or anisylcarbene synthons.
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