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Concomitant Nitrene and Carbene Insertion Accompanying Ring Expansion: Spectroscopic, X‑ray, and Computational Studies

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posted on 07.02.2014, 00:00 by Divneet Kaur, Hoi L. Luk, William Coldren, Pavan M. Srinivas, Lakshetti Sridhar, Sripadi Prabhakar, Partha Raghunathan, T. N. Guru Row, Christopher M. Hadad, Matthew S. Platz, Sambasivan V. Eswaran
Reinvestigation of the thermolysis of azido-meta-hemipinate (I) yielded, in addition to known II, unusual products III and IV. These products are formed via a rare intramolecular nitrene insertion into an adjacent methoxy C–H bond followed by an intermolecular reaction during a ring-expansion and a ring-extrusion reaction followed by a carbene insertion. The structures of the new compounds were confirmed using a battery of techniques, including HRMS (ESI-QTOF) and 2D NMR as well as X-ray crystallography for compound IV. Density functional theory methods were used to support the proposed mechanism of formation of the products.