Conclusive Evidence for a Retention−Retention Pathway for the Molybdenum-Catalyzed Asymmetric Alkylation
- 30 December 2003
- journal article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 126 (3), 702-703
- https://doi.org/10.1021/ja0376339
Abstract
Enantiomerically enriched, deuterated branched carbonates (Z)-(S)-PhCH(O2COMe)−CHCHD (1a), (Z)-(R)-PhCH(O2COMe)CHCHD (2a), and linear carbonate (E)-(S)-PhCHCHCHD(O2COMe) (12) were employed as probes in the Mo-catalyzed asymmetric allylic alkylation with sodium dimethyl malonate, catalyzed by ligand complex 10 derived from the mixed benzamide/picolinamide of (S,S)-trans-diaminocyclohexane and (norbornadiene)Mo(CO)4. X-ray crystallography, along with solution NMR structural analysis of the π-allyl intermediate and competition experiments, conclusively established the reaction proceeded via a retention−retention pathway. This mechanism contrasts with that defined for Pd-catalyzed allylic alkylations, which proceed via an inversion−inversion pathway.Keywords
This publication has 13 references indexed in Scilit:
- Stereochemistry of Molybdenum(0)-Catalyzed Allylic Substitution: The First Observation of a Syn-Syn MechanismJournal of the American Chemical Society, 1995
- Enantiospecific synthesis by transformations of chiral pool-derived metal .pi.-complexes. A strategy for the introduction of substituents on a pyranose-derived lateral .pi.-ligand either syn or anti to the coordinating metalJournal of the American Chemical Society, 1993
- Ligand dependence of molybdenum-catalyzed alkylations. Molybdenum-isonitrile complexes as a new class of highly reactive alkylation catalystsJournal of the American Chemical Society, 1990
- Reversal of stereochemical path in allylic alkylations promoted by palladium and molybdenum complexesOrganometallics, 1988
- Stereo- and regiochemistry in palladium-catalyzed nucleophilic substitution of optically active (E)- and (Z)-allyl acetatesThe Journal of Organic Chemistry, 1986
- Asymmetric synthesis. Mechanism of asymmetric catalytic allylationJournal of the American Chemical Society, 1985
- Stereochemistry of the reaction of an optically active π-allylpalladium complex with nucleophilesJournal of the Chemical Society, Chemical Communications, 1984
- Stereochemistry of oxidative addition of an optically active allyl acetate to a palladium(0) complexJournal of the American Chemical Society, 1983
- Allylic substitutions with retention of stereochemistryThe Journal of Organic Chemistry, 1976
- Regio- and stereoselectivity of allylic alkylationJournal of the American Chemical Society, 1975