Palladium(II)-catalyzed enyne coupling reaction initiated by acetoxypalladation of alkynes and quenched by protonolysis of the carbon-palladium bond.
J Org Chem. 2005 May 13; 70(10):4059-63.JO

Abstract

[reaction: see text] Divalent palladium-catalyzed inter- and intramolecular enyne coupling reactions initiated by acetoxypalladation of alkynes were developed. The reaction involves the acetoxypalladation of the alkyne, followed by the insertion of the alkene and the protonolysis of the carbon-palladium bond. The protonolysis of the carbon-palladium bond in the presence of bidentate nitrogen containing ligands is the key step in completing the Pd(II) catalytic cycle. The nitrogen-containing ligands, like halides, served to favor the protonolysis of the carbon-palladium bond over the beta-H elimination in the Pd(II)-mediated reactions. The intermolecular coupling reactions provide an efficient method for synthesizing gamma,delta-unsaturated carbonyls. The intramolecular coupling reactions offer a method to construct a variety of synthetically important carbo- and heterocycles. The asymmetric version of such a cyclization was developed with moderate enantioselectivity when employing pymox (pyridyl monooxazoline) as the ligand.

Authors+Show Affiliations

Zhao L

State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Lu, Shanghai, 200032, China.

Lu X

No affiliation info available

Xu W

No affiliation info available

Pub Type(s)

Journal Article

Language

eng

PubMed ID

15876097

Citation

Zhao, Ligang, et al. "Palladium(II)-catalyzed Enyne Coupling Reaction Initiated By Acetoxypalladation of Alkynes and Quenched By Protonolysis of the Carbon-palladium Bond." The Journal of Organic Chemistry, vol. 70, no. 10, 2005, pp. 4059-63.

Zhao L, Lu X, Xu W. Palladium(II)-catalyzed enyne coupling reaction initiated by acetoxypalladation of alkynes and quenched by protonolysis of the carbon-palladium bond. J Org Chem. 2005;70(10):4059-63.

Zhao, L., Lu, X., & Xu, W. (2005). Palladium(II)-catalyzed enyne coupling reaction initiated by acetoxypalladation of alkynes and quenched by protonolysis of the carbon-palladium bond. The Journal of Organic Chemistry, 70(10), 4059-63.

Zhao L, Lu X, Xu W. Palladium(II)-catalyzed Enyne Coupling Reaction Initiated By Acetoxypalladation of Alkynes and Quenched By Protonolysis of the Carbon-palladium Bond. J Org Chem. 2005 May 13;70(10):4059-63. PubMed PMID: 15876097.

* Article titles in AMA citation format should be in sentence-case

TY - JOUR T1 - Palladium(II)-catalyzed enyne coupling reaction initiated by acetoxypalladation of alkynes and quenched by protonolysis of the carbon-palladium bond. AU - Zhao,Ligang, AU - Lu,Xiyan, AU - Xu,Wei, PY - 2005/5/7/pubmed PY - 2005/5/7/medline PY - 2005/5/7/entrez SP - 4059 EP - 63 JF - The Journal of organic chemistry JO - J Org Chem VL - 70 IS - 10 N2 - [reaction: see text] Divalent palladium-catalyzed inter- and intramolecular enyne coupling reactions initiated by acetoxypalladation of alkynes were developed. The reaction involves the acetoxypalladation of the alkyne, followed by the insertion of the alkene and the protonolysis of the carbon-palladium bond. The protonolysis of the carbon-palladium bond in the presence of bidentate nitrogen containing ligands is the key step in completing the Pd(II) catalytic cycle. The nitrogen-containing ligands, like halides, served to favor the protonolysis of the carbon-palladium bond over the beta-H elimination in the Pd(II)-mediated reactions. The intermolecular coupling reactions provide an efficient method for synthesizing gamma,delta-unsaturated carbonyls. The intramolecular coupling reactions offer a method to construct a variety of synthetically important carbo- and heterocycles. The asymmetric version of such a cyclization was developed with moderate enantioselectivity when employing pymox (pyridyl monooxazoline) as the ligand. SN - 0022-3263 UR - https://www.unboundmedicine.com/medline/citation/15876097/Palladium_II__catalyzed_enyne_coupling_reaction_initiated_by_acetoxypalladation_of_alkynes_and_quenched_by_protonolysis_of_the_carbon_palladium_bond_ DB - PRIME DP - Unbound Medicine ER -

Tags

Palladium(II)-catalyzed enyne coupling reaction initiated by acetoxypalladation of alkynes and quenched by protonolysis of the carbon-palladium bond.J Org Chem. 2005 May 13; 70(10):4059-63.JO