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Palladium-catalyzed carbonylative cyclization of unsaturated aryl iodides and dienyl triflates, iodides, and bromides to indanones and 2-cyclopentenones.
J Am Chem Soc. 2003 Apr 23; 125(16):4804-7.JA

Abstract

Indanones and 2-cyclopentenones have been successfully prepared in good to excellent yields by the palladium-catalyzed carbonylative cyclization of unsaturated aryl iodides and dienyl triflates, iodides, and bromides, respectively. The best results are obtained by employing 10 mol % of Pd(OAc)(2), 2 equiv of pyridine, 1 equiv of n-Bu(4)NCl, 1 atm of CO, a reaction temperature of 100 degrees C, and DMF as the solvent. This carbonylative cyclization is particularly effective on substrates that contain a terminal olefin. The proposed mechanism for this annulation includes (1) Pd(OAc)(2) reduction to the active palladium(0) catalyst, (2) oxidative addition of the organic halide or triflate to Pd(0), (3) coordination and insertion of carbon monoxide to produce an acylpalladium intermediate, (4) acylpalladation of the neighboring carbon-carbon double bond, (5) reversible palladium beta-hydride elimination and re-addition to form a palladium enolate, and (6) protonation by H(2)O to produce the indanone or 2-cyclopentenone.

Authors+Show Affiliations

Gagnier SV
Department of Chemistry, Iowa State University, Ames, Iowa 50010, USA.
Larock RC
No affiliation info available

MeSH

AlkenesBromobenzenesCatalysisCyclizationCyclopentanesHydrocarbons, BrominatedHydrocarbons, IodinatedIndansIodobenzenesPalladium

Pub Type(s)

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

Language

eng

PubMed ID

12696899

Citation

Gagnier, Steve V., and Richard C. Larock. "Palladium-catalyzed Carbonylative Cyclization of Unsaturated Aryl Iodides and Dienyl Triflates, Iodides, and Bromides to Indanones and 2-cyclopentenones." Journal of the American Chemical Society, vol. 125, no. 16, 2003, pp. 4804-7.
Gagnier SV, Larock RC. Palladium-catalyzed carbonylative cyclization of unsaturated aryl iodides and dienyl triflates, iodides, and bromides to indanones and 2-cyclopentenones. J Am Chem Soc. 2003;125(16):4804-7.
Gagnier, S. V., & Larock, R. C. (2003). Palladium-catalyzed carbonylative cyclization of unsaturated aryl iodides and dienyl triflates, iodides, and bromides to indanones and 2-cyclopentenones. Journal of the American Chemical Society, 125(16), 4804-7.
Gagnier SV, Larock RC. Palladium-catalyzed Carbonylative Cyclization of Unsaturated Aryl Iodides and Dienyl Triflates, Iodides, and Bromides to Indanones and 2-cyclopentenones. J Am Chem Soc. 2003 Apr 23;125(16):4804-7. PubMed PMID: 12696899.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Palladium-catalyzed carbonylative cyclization of unsaturated aryl iodides and dienyl triflates, iodides, and bromides to indanones and 2-cyclopentenones. AU - Gagnier,Steve V, AU - Larock,Richard C, PY - 2003/4/17/pubmed PY - 2003/6/17/medline PY - 2003/4/17/entrez SP - 4804 EP - 7 JF - Journal of the American Chemical Society JO - J Am Chem Soc VL - 125 IS - 16 N2 - Indanones and 2-cyclopentenones have been successfully prepared in good to excellent yields by the palladium-catalyzed carbonylative cyclization of unsaturated aryl iodides and dienyl triflates, iodides, and bromides, respectively. The best results are obtained by employing 10 mol % of Pd(OAc)(2), 2 equiv of pyridine, 1 equiv of n-Bu(4)NCl, 1 atm of CO, a reaction temperature of 100 degrees C, and DMF as the solvent. This carbonylative cyclization is particularly effective on substrates that contain a terminal olefin. The proposed mechanism for this annulation includes (1) Pd(OAc)(2) reduction to the active palladium(0) catalyst, (2) oxidative addition of the organic halide or triflate to Pd(0), (3) coordination and insertion of carbon monoxide to produce an acylpalladium intermediate, (4) acylpalladation of the neighboring carbon-carbon double bond, (5) reversible palladium beta-hydride elimination and re-addition to form a palladium enolate, and (6) protonation by H(2)O to produce the indanone or 2-cyclopentenone. SN - 0002-7863 UR - https://www.unboundmedicine.com/medline/citation/12696899/Palladium_catalyzed_carbonylative_cyclization_of_unsaturated_aryl_iodides_and_dienyl_triflates_iodides_and_bromides_to_indanones_and_2_cyclopentenones_ DB - PRIME DP - Unbound Medicine ER -