title: Concomitant nitrene and carbene insertion accompanying ring expansion: spectroscopic, X-ray, and computational studies.
abstract: 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.
authors.affiliation: St. Stephen's College, University of Delhi , Delhi 110007, India.
authors.forename: Divneet
authors.initials: D
authors.lastname: Kaur
authors.forename: Hoi L
authors.initials: HL
authors.lastname: Luk
authors.forename: William
authors.initials: W
authors.lastname: Coldren
authors.forename: Pavan M
authors.initials: PM
authors.lastname: Srinivas
authors.forename: Lakshetti
authors.initials: L
authors.lastname: Sridhar
authors.forename: Sripadi
authors.initials: S
authors.lastname: Prabhakar
authors.forename: Partha
authors.initials: P
authors.lastname: Raghunathan
authors.forename: T N
authors.initials: TN
authors.lastname: Guru Row
authors.forename: Christopher M
authors.initials: CM
authors.lastname: Hadad
authors.forename: Matthew S
authors.initials: MS
authors.lastname: Platz
authors.forename: Sambasivan V
authors.initials: SV
authors.lastname: Eswaran
mesh_terms: D018360:Crystallography, X-Ray; D007097:Imines / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D011789:Quantum Theory
chemical_list: D007097:Imines; C030011:carbene; C017621:phenylnitrene; D008697:Methane