Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 132, Issue 34, Pages 11978-11987Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja1030936
Keywords
-
Categories
Funding
- Chinese Academy of Sciences
- National Nature Science Foundation of China [20821002, 20872155, 20972175, 20923005]
- National Basic Research Program of China [973-2009CB825300]
- Science and Technology Commission of the Shanghai Municipality [08PJ1411600, 08dj1400100]
Ask authors/readers for more resources
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.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available