On the mechanism of the ruthenium-catalyzed reconstitutive condensation of allylic alcohols and terminal alkynes
- Stanford Univ., CA (United States)
The ruthenium complex ({eta}{sup 5}-C{sub 5}H{sub 5})(PPh{sub 3}){sub 2}RuCl (1) catalyzes the addition of allytic alcohols to terminal alkynes, yielding {Beta}{gamma}-unsaturated ketones. The intermediacy of a ruthenium vinylidene complex is indicated by the synthesis of this proposed intermediate and the demonstration of the same reaction profile as with catalyst 1. Loss of terminal deuterium in labeled alkynes supports this conclusion. Ligand substitution studies demonstrate the necessity of phosphine loss and precoordination of the allylic alcohol. Deuterium labeling of allyl alcohol demonstrates that the two allylic termini do not become equivalent and that the olefin geometry does not scramble. In contrast to these observations, 3-buten-2-ol shows complete regioselectivity in the condensation but randomization of olefin geometry as determined by deuterium labeling. A cohesive mechanistic rationale accommodates these seemingly disparate observations. 24 refs., 4 figs.
- Sponsoring Organization:
- USDOE
- OSTI ID:
- 229929
- Journal Information:
- Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 14 Vol. 114; ISSN JACSAT; ISSN 0002-7863
- Country of Publication:
- United States
- Language:
- English
Similar Records
Hydroformylation of allyl alcohol in the presence of modified rhodium catalysts
(CAAC)Copper Catalysis Enables Regioselective Three-Component Carboboration of Terminal Alkynes