ISSN:
0009-2940
Keywords:
Vinylidene complexes
;
Allenylidene complexes
;
Ene type reactions
;
Atom economial reactions
;
Reconstitutive additions
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Ruthenium complexes catalyze a variety of addition or isomerization reactions that are highly atom economical. Terminal alkynes react with allyl alcohols to form β,γ-unsaturated ketones that can be readily isomerized to α,β-unsaturated ketones via transient vinylidene complexes. A cyclization via a transient allenylidene complex concomitant with this addition represents a novel way to build heterocycles. Ancillary studies with these catalysts revealed an internal oxidation reduction whereby allyl alcohols are isomerized to saturated ketones and propargyl alcohols are isomerized to α,β-unsaturated carbonyl compounds. Consideration of the reaction mechanism led to a general Alder ene type reaction wherein alkynes serve as the enophile and alkenes serve as the ene component. These discoveries have led to a number of efficient total syntheses of biologically interesting targets. Mechanistic investigations into the activation of a ruthenium complex led to the discovery of a novel bis-homo-Diels-Alder reaction of 1,4-cyclooctadiene.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19961291102
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