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Catalytic carbonyl Z-dienylation via multicomponent reductive coupling of acetylene to aldehydes and alpha-ketoesters mediated by hydrogen: Carbonyl insertion into cationic rhodacyclopentadienes.
J Am Chem Soc. 2006 Dec 20; 128(50):16040-1.JA

Abstract

Exposure of aldehydes or alpha-ketoesters to equal volumes of acetylene and hydrogen gas at ambient temperature and pressure in the presence of cationic rhodium catalysts provides products of carbonyl Z-butadienylation, which arise via multicomponent coupling of four molecules: two molecules of acetylene, a molecule of vicinal dicarbonyl compound, and a molecule of elemental hydrogen. The collective data suggest a catalytic mechanism involving carbonyl insertion into a cationic rhodacyclopentadiene intermediate derived via oxidative dimerization of acetylene. Hydrogenolytic cleavage of the resulting oxarhodacycloheptadiene via formal sigma-bond metathesis provides the product of carbonyl addition and cationic rhodium(I) to close the catalytic cycle. Studies involving the hydrogenation of 1,6-diyne 14a in the presence of alpha-ketoester 6a corroborate the proposed catalytic mechanism. These multicomponent couplings represent the first use of acetylene gas, a basic chemical feedstock, in metal-catalyzed reductive C-C bond formation.

Authors+Show Affiliations

Department of Chemistry and Biochemistry, University of Texas at Austin, Austin, Texas 78712, USA.No affiliation info available

Pub Type(s)

Journal Article
Research Support, N.I.H., Extramural
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

17165749

Citation

Kong, Jong Rock, and Michael J. Krische. "Catalytic Carbonyl Z-dienylation Via Multicomponent Reductive Coupling of Acetylene to Aldehydes and Alpha-ketoesters Mediated By Hydrogen: Carbonyl Insertion Into Cationic Rhodacyclopentadienes." Journal of the American Chemical Society, vol. 128, no. 50, 2006, pp. 16040-1.
Kong JR, Krische MJ. Catalytic carbonyl Z-dienylation via multicomponent reductive coupling of acetylene to aldehydes and alpha-ketoesters mediated by hydrogen: Carbonyl insertion into cationic rhodacyclopentadienes. J Am Chem Soc. 2006;128(50):16040-1.
Kong, J. R., & Krische, M. J. (2006). Catalytic carbonyl Z-dienylation via multicomponent reductive coupling of acetylene to aldehydes and alpha-ketoesters mediated by hydrogen: Carbonyl insertion into cationic rhodacyclopentadienes. Journal of the American Chemical Society, 128(50), 16040-1.
Kong JR, Krische MJ. Catalytic Carbonyl Z-dienylation Via Multicomponent Reductive Coupling of Acetylene to Aldehydes and Alpha-ketoesters Mediated By Hydrogen: Carbonyl Insertion Into Cationic Rhodacyclopentadienes. J Am Chem Soc. 2006 Dec 20;128(50):16040-1. PubMed PMID: 17165749.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Catalytic carbonyl Z-dienylation via multicomponent reductive coupling of acetylene to aldehydes and alpha-ketoesters mediated by hydrogen: Carbonyl insertion into cationic rhodacyclopentadienes. AU - Kong,Jong Rock, AU - Krische,Michael J, PY - 2006/12/15/pubmed PY - 2007/2/21/medline PY - 2006/12/15/entrez SP - 16040 EP - 1 JF - Journal of the American Chemical Society JO - J Am Chem Soc VL - 128 IS - 50 N2 - Exposure of aldehydes or alpha-ketoesters to equal volumes of acetylene and hydrogen gas at ambient temperature and pressure in the presence of cationic rhodium catalysts provides products of carbonyl Z-butadienylation, which arise via multicomponent coupling of four molecules: two molecules of acetylene, a molecule of vicinal dicarbonyl compound, and a molecule of elemental hydrogen. The collective data suggest a catalytic mechanism involving carbonyl insertion into a cationic rhodacyclopentadiene intermediate derived via oxidative dimerization of acetylene. Hydrogenolytic cleavage of the resulting oxarhodacycloheptadiene via formal sigma-bond metathesis provides the product of carbonyl addition and cationic rhodium(I) to close the catalytic cycle. Studies involving the hydrogenation of 1,6-diyne 14a in the presence of alpha-ketoester 6a corroborate the proposed catalytic mechanism. These multicomponent couplings represent the first use of acetylene gas, a basic chemical feedstock, in metal-catalyzed reductive C-C bond formation. SN - 0002-7863 UR - https://www.unboundmedicine.com/medline/citation/17165749/Catalytic_carbonyl_Z_dienylation_via_multicomponent_reductive_coupling_of_acetylene_to_aldehydes_and_alpha_ketoesters_mediated_by_hydrogen:_Carbonyl_insertion_into_cationic_rhodacyclopentadienes_ L2 - https://doi.org/10.1021/ja0664786 DB - PRIME DP - Unbound Medicine ER -