Organic Letters
Letter
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Scheme 7. Access to Azepanes 32 and 33
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from 2H-azirines through a stepwise annulation process. These
latter azabicyclic compounds can be functionalized and
undergo regioselective ring opening with carboxylic acids or
sulfur nucleophiles to afford azepanones possessing an ester
functional group or a trifluoromethyl substituent at the α
position of the nitrogen atom as well as a tetrasubstituted
carbon atom at the β position. This work complements the
current knowledge of regioselective ring-opening reactions
involving bicyclic aziridines and further highlights the interest
of strained ring-cleavage strategies as a route to seven-
membered nitrogen heterocycles. Other applications of these
processes are currently under investigation.
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ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
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S
Experimental procedures, characterization data, and
spectra for all new compounds (PDF)
Accession Codes
CCDC 1900066 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge
bridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
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Angew. Chem., Int. Ed. 2009, 48, 3802−3805. (g) Malik, G.; Esteoule,
A.; Retailleau, P.; Dauban, P. J. Org. Chem. 2011, 76, 7438−7448.
(h) Rigoli, J. W.; Boralsky, L. A.; Hershberger, J. C.; Marston, D.;
Meis, A. R.; Guzei, I. A.; Schomaker, J. M. J. Org. Chem. 2012, 77,
2446−2455. (i) Goto, A.; Yoshimura, S.; Nakao, Y.; Inai, M.;
Asakawa, T.; Egi, M.; Hamashima, Y.; Kondo, M.; Kan, T. Org. Lett.
2017, 19, 3358−3361.
(13) One previous example of a substrate of type G, unsubstituted at
C1, has been reported. Subsequent nucleophilic additions occur either
at C1 or on the carbonyl group: Wu, X.; Toppet, S.; Compernolle, F.;
Hoornaert, G. J. Tetrahedron 2003, 59, 1483−1491.
AUTHOR INFORMATION
Corresponding Authors
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ORCID
(14) Ring opening of aziridines under these conditions occurs at the
carbon best able to stabilize a positive charge. For examples, see:
(a) Berse, C.; Bessette, P. Can. J. Chem. 1971, 49, 2610−2611.
(b) Takeuchi, H.; Koyama, K. J. Chem. Soc., Perkin Trans. 2 1981,
121−126. (c) Quinze, K.; Laurent, A.; Mison, P. J. Fluorine Chem.
1989, 44, 233−265. (d) Legters, J.; Willems, J. G. H.; Thijs, L.;
Zwanenburg, B. Recl. Trav. Chim. Pays-Bas 1992, 111, 59−68.
(e) Righi, G.; D’Achille, R.; Bonini, C. Tetrahedron Lett. 1996, 37,
6893−6896. (f) Davoli, P.; Forni, A.; Franciosi, C.; Moretti, I.; Prati,
F. Tetrahedron: Asymmetry 1999, 10, 2361−2371. (g) Papa, C.;
Tomasini, C. Eur. J. Org. Chem. 2000, 2000, 1569−1576. (h) Crousse,
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
A.D. thanks PCAS for a CIFRE grant.
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