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Title: Ambimodal Bispericyclic [6 + 4]/[4 + 6] Transition State Competes with Diradical Pathways in the Cycloheptatriene Dimerization: Dynamics and Experimental Characterization of Thermal Dimers
Award ID(s):
1764328 2153972
PAR ID:
10412567
Author(s) / Creator(s):
; ; ; ;
Date Published:
Journal Name:
Journal of the American Chemical Society
Volume:
144
Issue:
48
ISSN:
0002-7863
Page Range / eLocation ID:
22251 to 22261
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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  1. Abstract Huisgen's 1960 announcement of the concept of 1,3‐dipolar cycloadditions was published the year before Alder's study of the reaction of diazomethane and dimethylfulvene. The diazomethane reaction was studied again in 1970 by Houk et al. and shown to give a [6+4] adduct. Padwa's nitrile ylide cycloaddition to dimethylfulvene (1978) gave [6+4] and [4+2] adducts. We performed computational studies of these reactions with density functional theory (DFT) and show that they involve ambimodal [6+4]/[4+2] transition states that can lead to either type of cycloadduct from one transition state. We dedicate this paper to the extraordinary life and humanity of Rolf Huisgen, and to the undying influence of his discoveries on chemistry. 
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