Propargylic oxidation catalyzed by dirhodium caprolactamate: Rapid access to α,β-acetylenic ketones

AEI 97

Emily C. McLaughlin, mclaughe@umd.edu and Michael P. Doyle. Department of Chemistry and Biochemistry, University of Maryland, College Park, MD 20742
Dirhodium(II) caprolactamate (1), Rh2(cap)4, is a highly effective catalyst for C-H oxidation when paired with t-butyl hydroperoxide (t-BuOOH). Using this catalytic system, allylic, benzylic, and secondary amine oxidations have been reported. For this work, alternate reaction conditions, including the use of water as an ‘environmentally friendly' solvent, are explored. Consequently, the scope of C-H oxidation can be expanded to include propargylic substrates to form α,β-acetylenic carbonyl compounds. Most reactions are performed at ambient temperature and all employ an inexpensive and easy to handle oxidant, T-HYDRO® (70% t-BuOOH in water). The breadth of propargylic oxidation and synthetic applications of α,β-acetylenic ketones are also reported.

 

Academic Employment Initiative
8:00 PM-10:00 PM, Monday, August 20, 2007 BCEC -- Exhibit Hall - B2, Sci-Mix

Academic Employment Initiative

The 234th ACS National Meeting, Boston, MA, August 19-23, 2007