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Synthesis and application of chiral cyclopropane-based ligands in palladium-catalyzed allylic alkylation.
J Org Chem. 2004 Nov 12; 69(23):8062-9.JO

Abstract

A series of chiral, cyclopropane-based phosphorus/sulfur ligands have been synthesized and evaluated in the palladium-catalyzed allylic alkylation of 1,3-diphenylpropenyl acetate with dimethyl malonate. Variation of the ligand substituents at phosphorus, sulfur, and the carbon backbone revealed 24d to have the optimal configuration for this reaction, giving the product in high yield and with good enantioselectivity (93%). A model for the observed enantioselectivity is discussed within the context of existing models, using X-ray crystallographic data, solution-phase NMR studies, and the absolute stereochemistry of the products. Selected ligands were also evaluated in the palladium-catalyzed intermolecular Heck reaction and the rhodium-catalyzed hydrogenation of a dehydroamino acid.

Authors+Show Affiliations

Roy and Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323, USA. gmolandr@sas.upenn.eduNo affiliation info availableNo affiliation info available

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

15527291

Citation

Molander, Gary A., et al. "Synthesis and Application of Chiral Cyclopropane-based Ligands in Palladium-catalyzed Allylic Alkylation." The Journal of Organic Chemistry, vol. 69, no. 23, 2004, pp. 8062-9.
Molander GA, Burke JP, Carroll PJ. Synthesis and application of chiral cyclopropane-based ligands in palladium-catalyzed allylic alkylation. J Org Chem. 2004;69(23):8062-9.
Molander, G. A., Burke, J. P., & Carroll, P. J. (2004). Synthesis and application of chiral cyclopropane-based ligands in palladium-catalyzed allylic alkylation. The Journal of Organic Chemistry, 69(23), 8062-9.
Molander GA, Burke JP, Carroll PJ. Synthesis and Application of Chiral Cyclopropane-based Ligands in Palladium-catalyzed Allylic Alkylation. J Org Chem. 2004 Nov 12;69(23):8062-9. PubMed PMID: 15527291.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Synthesis and application of chiral cyclopropane-based ligands in palladium-catalyzed allylic alkylation. AU - Molander,Gary A, AU - Burke,Jason P, AU - Carroll,Patrick J, PY - 2004/11/6/pubmed PY - 2004/12/24/medline PY - 2004/11/6/entrez SP - 8062 EP - 9 JF - The Journal of organic chemistry JO - J Org Chem VL - 69 IS - 23 N2 - A series of chiral, cyclopropane-based phosphorus/sulfur ligands have been synthesized and evaluated in the palladium-catalyzed allylic alkylation of 1,3-diphenylpropenyl acetate with dimethyl malonate. Variation of the ligand substituents at phosphorus, sulfur, and the carbon backbone revealed 24d to have the optimal configuration for this reaction, giving the product in high yield and with good enantioselectivity (93%). A model for the observed enantioselectivity is discussed within the context of existing models, using X-ray crystallographic data, solution-phase NMR studies, and the absolute stereochemistry of the products. Selected ligands were also evaluated in the palladium-catalyzed intermolecular Heck reaction and the rhodium-catalyzed hydrogenation of a dehydroamino acid. SN - 0022-3263 UR - https://www.unboundmedicine.com/medline/citation/15527291/Synthesis_and_application_of_chiral_cyclopropane_based_ligands_in_palladium_catalyzed_allylic_alkylation_ L2 - https://doi.org/10.1021/jo048782s DB - PRIME DP - Unbound Medicine ER -