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Development of catalytic asymmetric reactions via chiral palladium enolates.
Chem Rec. 2004; 4(4):231-42.CR

Abstract

This article describes the generation of chiral palladium enolates and their application to several kinds of catalytic asymmetric reactions. Two methods to generate chiral enolates were developed using novel cationic palladium complexes 1 and 2. In these processes, water or a hydroxo ligand on palladium metal plays an important role as a nucleophile to promote the transmetallation or as a Brønsted base to abstract an acidic alpha-proton of the carbonyl group. These enolates showed sufficient reactivity with various electrophiles. Using a chiral Pd enolate as a key intermediate, highly enantioselective reactions such as catalytic aldol reactions, Mannich-type reactions, Michael reactions, and fluorination reactions were developed. The unique structures of the palladium enolate complexes were elucidated and reaction mechanisms are proposed.

Authors+Show Affiliations

Hamashima Y
Institute of Multidisciplinary Research for Advanced Materials, Tohoku University, Katahira, Sendai, Miyagi 980-8577, Japan.
Sodeoka M
No affiliation info available

MeSH

AldehydesCatalysisEstersKetonesModels, ChemicalMolecular ConformationMolecular StructureOrganometallic CompoundsPalladiumStereoisomerism

Pub Type(s)

Journal Article

Language

eng

PubMed ID

15340908

Citation

Hamashima, Yoshitaka, and Mikiko Sodeoka. "Development of Catalytic Asymmetric Reactions Via Chiral Palladium Enolates." Chemical Record (New York, N.Y.), vol. 4, no. 4, 2004, pp. 231-42.
Hamashima Y, Sodeoka M. Development of catalytic asymmetric reactions via chiral palladium enolates. Chem Rec. 2004;4(4):231-42.
Hamashima, Y., & Sodeoka, M. (2004). Development of catalytic asymmetric reactions via chiral palladium enolates. Chemical Record (New York, N.Y.), 4(4), 231-42.
Hamashima Y, Sodeoka M. Development of Catalytic Asymmetric Reactions Via Chiral Palladium Enolates. Chem Rec. 2004;4(4):231-42. PubMed PMID: 15340908.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Development of catalytic asymmetric reactions via chiral palladium enolates. AU - Hamashima,Yoshitaka, AU - Sodeoka,Mikiko, PY - 2004/9/2/pubmed PY - 2004/12/16/medline PY - 2004/9/2/entrez SP - 231 EP - 42 JF - Chemical record (New York, N.Y.) JO - Chem Rec VL - 4 IS - 4 N2 - This article describes the generation of chiral palladium enolates and their application to several kinds of catalytic asymmetric reactions. Two methods to generate chiral enolates were developed using novel cationic palladium complexes 1 and 2. In these processes, water or a hydroxo ligand on palladium metal plays an important role as a nucleophile to promote the transmetallation or as a Brønsted base to abstract an acidic alpha-proton of the carbonyl group. These enolates showed sufficient reactivity with various electrophiles. Using a chiral Pd enolate as a key intermediate, highly enantioselective reactions such as catalytic aldol reactions, Mannich-type reactions, Michael reactions, and fluorination reactions were developed. The unique structures of the palladium enolate complexes were elucidated and reaction mechanisms are proposed. SN - 1527-8999 UR - https://www.unboundmedicine.com/medline/citation/15340908/Development_of_catalytic_asymmetric_reactions_via_chiral_palladium_enolates_ DB - PRIME DP - Unbound Medicine ER -