Journal of the American Chemical Society
COMMUNICATION
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Figure 2. Plausible mechanism for oxidative rearrangement.
Scheme 1. Utility of Products from [2,3]-Rearrangementa
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a Conditions: (i) Zn, AcOH; (ii) HCl, dioxanes; PtO2, H2; AcCl, Et3N,
DMAP; (iii) MeMgCl or PhMgCl, THF; (iv) toluene, reflux.
readily upon mild heating in toluene to afford β,γ-unsaturated
ester 17 in 96% yield.
In summary, we have developed an efficient and high yielding
oxidative [2,3]-sigmatropic rearrangement of allylic hydrazides, and
demonstrated the utility of the diazene products obtained. Complete
stereochemical transfer when an enantioenriched hydrazide was
used provides a new method to access nonracemic tertiary carbina-
mine derivatives. In recent years there have been many significant
advances in enantioselective nitrene-type transformations,18 and
although our oxidative [2,3]-rearrangement does not require
transition-metal additives, it still seems reasonable to suggest that
a catalytic enantioselective variant may be developed in the future.19
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’ ASSOCIATED CONTENT
S
Supporting Information. Detailed experimental proce-
b
dures and spectral data for all compounds. This material is
(11) For a review on the decomposition of azoalkanes, see:Engel,
P. S. Chem. Rev. 1980, 80, 99–150.
’ AUTHOR INFORMATION
Corresponding Author
(12) Natsugari, H.; Turos, E.; Weinreb, S. M.; Cvetovich, R. J.
Heterocycles 1987, 25, 19–24. For related studies of [2,3]-sigmatropic
rearrangements forming carbonÀcarbon bonds, see: (a) G. Andrews,
G.; Evans, D. A. Tetrahedron Lett. 1972, 5121. (b) Mander, L. N.;
Turner, J. V. J. Org. Chem. 1973, 38, 2915–2916. (c) Evans, D. A.; Sims,
C. L.; Andrews, G. C. J. Am. Chem. Soc. 1977, 99, 5453–5461.
(13) Full experimental details may be found in the Supporting
Information.
’ ACKNOWLEDGMENT
We gratefully acknowledge support from the National
Science Foundation (CHE0845063 and CHE0923236),
Amgen Inc., Dow Chemical Company and Northwestern
University. We thank Reed Larson (NU) for X-ray analysis of
compound 11.
(14) Alkyl, aryl and carbonyl nitrenes are known to have triplet
ground states, while N-aminonitrenes have singlet ground states, see:
(a) Berry, R. S. In Nitrenes; Lwowski, W., Ed.; Interscience: New York,
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dx.doi.org/10.1021/ja2066219 |J. Am. Chem. Soc. 2011, 133, 14252–14255