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Regioselective and enantiospecific rhodium-catalyzed allylic alkylation reactions using copper(I) enolates: synthesis of (-)-sugiresinol dimethyl ether.
J Am Chem Soc. 2003 Jul 30; 125(30):8974-5.JA

Abstract

The transition metal-catalyzed allylic alkylation represents a fundamentally important cross-coupling reaction for the construction of ternary carbon stereogenic centers. We have developed a regioselective and enantiospecific rhodium-catalyzed allylic alkylation of acyclic unsymmetrical allylic alcohol derivatives using copper(I) enolates to prepare beta-substituted ketones. This protocol represents a convenient asymmetric Claisen rearrangement surrogate in which alpha-substituted enolates permit the introduction of an additional stereogenic center. The synthetic utility of this transformation was highlighted in the construction of a trans-1,2-disubstituted cyclohexene and the total synthesis of (-)-sugiresinol dimethyl ether. Finally, we anticipate that copper(I) enolates may prove useful nucleophiles in related metal-catalyzed reactions.

Authors+Show Affiliations

Evans PA
Department of Chemistry, Indiana University, Bloomington, IN 47405, USA. paevans@indiana.edu
Leahy DK
No affiliation info available

MeSH

AlkylationAllyl CompoundsCatalysisCopperCryptomeriaEstersLignansOrganometallic CompoundsPropanolsRhodiumStereoisomerism

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, P.H.S.

Language

eng

PubMed ID

15369328

Citation

Evans, P Andrew, and David K. Leahy. "Regioselective and Enantiospecific Rhodium-catalyzed Allylic Alkylation Reactions Using copper(I) Enolates: Synthesis of (-)-sugiresinol Dimethyl Ether." Journal of the American Chemical Society, vol. 125, no. 30, 2003, pp. 8974-5.
Evans PA, Leahy DK. Regioselective and enantiospecific rhodium-catalyzed allylic alkylation reactions using copper(I) enolates: synthesis of (-)-sugiresinol dimethyl ether. J Am Chem Soc. 2003;125(30):8974-5.
Evans, P. A., & Leahy, D. K. (2003). Regioselective and enantiospecific rhodium-catalyzed allylic alkylation reactions using copper(I) enolates: synthesis of (-)-sugiresinol dimethyl ether. Journal of the American Chemical Society, 125(30), 8974-5.
Evans PA, Leahy DK. Regioselective and Enantiospecific Rhodium-catalyzed Allylic Alkylation Reactions Using copper(I) Enolates: Synthesis of (-)-sugiresinol Dimethyl Ether. J Am Chem Soc. 2003 Jul 30;125(30):8974-5. PubMed PMID: 15369328.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Regioselective and enantiospecific rhodium-catalyzed allylic alkylation reactions using copper(I) enolates: synthesis of (-)-sugiresinol dimethyl ether. AU - Evans,P Andrew, AU - Leahy,David K, PY - 2004/9/17/pubmed PY - 2004/11/13/medline PY - 2004/9/17/entrez SP - 8974 EP - 5 JF - Journal of the American Chemical Society JO - J Am Chem Soc VL - 125 IS - 30 N2 - The transition metal-catalyzed allylic alkylation represents a fundamentally important cross-coupling reaction for the construction of ternary carbon stereogenic centers. We have developed a regioselective and enantiospecific rhodium-catalyzed allylic alkylation of acyclic unsymmetrical allylic alcohol derivatives using copper(I) enolates to prepare beta-substituted ketones. This protocol represents a convenient asymmetric Claisen rearrangement surrogate in which alpha-substituted enolates permit the introduction of an additional stereogenic center. The synthetic utility of this transformation was highlighted in the construction of a trans-1,2-disubstituted cyclohexene and the total synthesis of (-)-sugiresinol dimethyl ether. Finally, we anticipate that copper(I) enolates may prove useful nucleophiles in related metal-catalyzed reactions. SN - 0002-7863 UR - https://www.unboundmedicine.com/medline/citation/15369328/Regioselective_and_enantiospecific_rhodium_catalyzed_allylic_alkylation_reactions_using_copper_I__enolates:_synthesis_of_____sugiresinol_dimethyl_ether_ DB - PRIME DP - Unbound Medicine ER -