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Synthesis of chiral chromans by the Pd-catalyzed asymmetric allylic alkylation (AAA): scope, mechanism, and applications.
J Am Chem Soc. 2004 Sep 29; 126(38):11966-83.JA

Abstract

The Pd-catalyzed asymmetric allylic alkylation (AAA) of phenol allyl carbonates serves as an efficient strategy to construct the allylic C-O bond allowing access to chiral chromans in up to 98% ee. The effect of pH and the influence of olefin geometry, as well as substitution pattern on the ee and the absolute configuration of the chiral chromans were explored in detail. These observations suggest a mechanism involving the cyclization of the more reactive pi-allyl palladium diastereomeric intermediate as the enantiodiscriminating step (Curtin-Hammett conditions). This methodology led to the enantioselective synthesis of the vitamin E core, the first enantioselective total synthesis of (+)-clusifoliol and (-)-siccanin, and the synthesis of an advanced intermediate toward (+)-rhododaurichromanic acid A.

Authors+Show Affiliations

Trost BM
Department of Chemistry, Stanford University, Stanford, California 94305-5080, USA. bmtrost@stanford.edu
Shen HC
No affiliation info available
Dong L
No affiliation info available
Surivet JP
No affiliation info available
Sylvain C
No affiliation info available

MeSH

AlkylationAllyl CompoundsCarbonatesCatalysisChromansMolecular ConformationPalladiumPhenolsStereoisomerismXanthenes

Pub Type(s)

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

Language

eng

PubMed ID

15382932

Citation

Trost, Barry M., et al. "Synthesis of Chiral Chromans By the Pd-catalyzed Asymmetric Allylic Alkylation (AAA): Scope, Mechanism, and Applications." Journal of the American Chemical Society, vol. 126, no. 38, 2004, pp. 11966-83.
Trost BM, Shen HC, Dong L, et al. Synthesis of chiral chromans by the Pd-catalyzed asymmetric allylic alkylation (AAA): scope, mechanism, and applications. J Am Chem Soc. 2004;126(38):11966-83.
Trost, B. M., Shen, H. C., Dong, L., Surivet, J. P., & Sylvain, C. (2004). Synthesis of chiral chromans by the Pd-catalyzed asymmetric allylic alkylation (AAA): scope, mechanism, and applications. Journal of the American Chemical Society, 126(38), 11966-83.
Trost BM, et al. Synthesis of Chiral Chromans By the Pd-catalyzed Asymmetric Allylic Alkylation (AAA): Scope, Mechanism, and Applications. J Am Chem Soc. 2004 Sep 29;126(38):11966-83. PubMed PMID: 15382932.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Synthesis of chiral chromans by the Pd-catalyzed asymmetric allylic alkylation (AAA): scope, mechanism, and applications. AU - Trost,Barry M, AU - Shen,Hong C, AU - Dong,Li, AU - Surivet,Jean-Philippe, AU - Sylvain,Catherine, PY - 2004/9/24/pubmed PY - 2005/5/3/medline PY - 2004/9/24/entrez SP - 11966 EP - 83 JF - Journal of the American Chemical Society JO - J Am Chem Soc VL - 126 IS - 38 N2 - The Pd-catalyzed asymmetric allylic alkylation (AAA) of phenol allyl carbonates serves as an efficient strategy to construct the allylic C-O bond allowing access to chiral chromans in up to 98% ee. The effect of pH and the influence of olefin geometry, as well as substitution pattern on the ee and the absolute configuration of the chiral chromans were explored in detail. These observations suggest a mechanism involving the cyclization of the more reactive pi-allyl palladium diastereomeric intermediate as the enantiodiscriminating step (Curtin-Hammett conditions). This methodology led to the enantioselective synthesis of the vitamin E core, the first enantioselective total synthesis of (+)-clusifoliol and (-)-siccanin, and the synthesis of an advanced intermediate toward (+)-rhododaurichromanic acid A. SN - 0002-7863 UR - https://www.unboundmedicine.com/medline/citation/15382932/Synthesis_of_chiral_chromans_by_the_Pd_catalyzed_asymmetric_allylic_alkylation__AAA_:_scope_mechanism_and_applications_ DB - PRIME DP - Unbound Medicine ER -