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Scope and mechanism of allylic C-H amination of terminal alkenes by the palladium/PhI(OPiv)2 catalyst system: insights into the effect of naphthoquinone.
J Am Chem Soc. 2010 Sep 01; 132(34):11978-87.JA

Abstract

Palladium-catalyzed oxidative amination of unactivated alkyl olefins has been developed to produce linear (E)-allylimides with high regioselectivity. This highly efficient transformation of alkenes has been achieved by enhancing the reoxidation of palladium with the strong oxidant PhI(OPiv)(2). The present work also provides the first systematic analysis of the mechanism of the allylic C-H oxidative amination. It has been found that naphthoquinone (NQ) plays a vital role in promoting olefin coordination to the palladium catalyst: in the absence of NQ, the turnover-limiting step is olefin coordination to palladium catalyst; in the presence of NQ, the reaction involves a rapid equilibration to give a nitrogen-coordinated olefin-Pd(NQ) complex that undergoes turnover-limiting allylic C-H bond activation to generate a pi-allyl-Pd intermediate. This work provides valuable insights for further studies on the functionalization of unactivated olefins.

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Publisher Full Text (DOI)

Authors+Show Affiliations

Yin G
State Key Laboratory of Organometallics Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Road, Shanghai, China 200032.
Wu Y
No affiliation info available
Liu G
No affiliation info available

MeSH

AlkenesAminationAminesCatalysisCoordination ComplexesMolecular StructureNaphthoquinonesPalladium

Pub Type(s)

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

Language

eng

PubMed ID

20690676

Citation

Yin, Guoyin, et al. "Scope and Mechanism of Allylic C-H Amination of Terminal Alkenes By the palladium/PhI(OPiv)2 Catalyst System: Insights Into the Effect of Naphthoquinone." Journal of the American Chemical Society, vol. 132, no. 34, 2010, pp. 11978-87.
Yin G, Wu Y, Liu G. Scope and mechanism of allylic C-H amination of terminal alkenes by the palladium/PhI(OPiv)2 catalyst system: insights into the effect of naphthoquinone. J Am Chem Soc. 2010;132(34):11978-87.
Yin, G., Wu, Y., & Liu, G. (2010). Scope and mechanism of allylic C-H amination of terminal alkenes by the palladium/PhI(OPiv)2 catalyst system: insights into the effect of naphthoquinone. Journal of the American Chemical Society, 132(34), 11978-87. https://doi.org/10.1021/ja1030936
Yin G, Wu Y, Liu G. Scope and Mechanism of Allylic C-H Amination of Terminal Alkenes By the palladium/PhI(OPiv)2 Catalyst System: Insights Into the Effect of Naphthoquinone. J Am Chem Soc. 2010 Sep 1;132(34):11978-87. PubMed PMID: 20690676.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Scope and mechanism of allylic C-H amination of terminal alkenes by the palladium/PhI(OPiv)2 catalyst system: insights into the effect of naphthoquinone. AU - Yin,Guoyin, AU - Wu,Yichen, AU - Liu,Guosheng, PY - 2010/8/10/entrez PY - 2010/8/10/pubmed PY - 2010/12/14/medline SP - 11978 EP - 87 JF - Journal of the American Chemical Society JO - J Am Chem Soc VL - 132 IS - 34 N2 - Palladium-catalyzed oxidative amination of unactivated alkyl olefins has been developed to produce linear (E)-allylimides with high regioselectivity. This highly efficient transformation of alkenes has been achieved by enhancing the reoxidation of palladium with the strong oxidant PhI(OPiv)(2). The present work also provides the first systematic analysis of the mechanism of the allylic C-H oxidative amination. It has been found that naphthoquinone (NQ) plays a vital role in promoting olefin coordination to the palladium catalyst: in the absence of NQ, the turnover-limiting step is olefin coordination to palladium catalyst; in the presence of NQ, the reaction involves a rapid equilibration to give a nitrogen-coordinated olefin-Pd(NQ) complex that undergoes turnover-limiting allylic C-H bond activation to generate a pi-allyl-Pd intermediate. This work provides valuable insights for further studies on the functionalization of unactivated olefins. SN - 1520-5126 UR - https://www.unboundmedicine.com/medline/citation/20690676/Scope_and_mechanism_of_allylic_C_H_amination_of_terminal_alkenes_by_the_palladium/PhI_OPiv_2_catalyst_system:_insights_into_the_effect_of_naphthoquinone_ L2 - https://doi.org/10.1021/ja1030936 DB - PRIME DP - Unbound Medicine ER -