ORGANIC
LETTERS
2013
Vol. 15, No. 10
2374–2377
Synthesis of 3‑Aza-bicyclo[3.1.0]hexan-
2-one Derivatives via Gold-Catalyzed
Oxidative Cyclopropanation of
N‑Allylynamides
Kai-Bing Wang, Rui-Qiao Ran, Shi-Dong Xiu, and Chuan-Ying Li*
Department of Chemistry, Zhejiang Sci-Tech University, Xiasha West Higher Education
District, Hangzhou 310018, China
Received March 21, 2013
ABSTRACT
N-Allylynamides with various functional groups and different substitution patterns can be converted into 3-aza-bicyclo[3.1.0]hexan-2-one
derivatives in moderate to high yield using IMesAuCl/AgBF4 as the catalyst and pyridine N-oxide as the oxidant. A noncarbene mediated approach
is proposed as the mechanism.
Metal carbenes are versatile intermediates in modern
synthetic chemistry.1 Recently, gold carbenes derived from
alkynes and leaving-group-bearing nucleophiles have
attracted considerable attention.2 In 2007, Toste3a and
Zhang3b reported that a gold activated alkyne could be
trapped by a tethered sulfoxide to afford a gold carbene
conveniently. On the basis of these pioneering works,
many new transformations such as XꢀH (X = C, O, N)
insertion,3 cycloaddition,4 β-hydride migration,5 ylide
formation,6 and rearrangement7 have been realized since
then. In 2011, we reported an efficient process to oxidize
alkynes to 1,2-dicarbonyl compounds using diphenyl sulf-
oxide as the mild oxidant.8 During the reaction scope
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r
10.1021/ol4007629
Published on Web 05/07/2013
2013 American Chemical Society