By Jie Jack Li, E. J. Corey
Content material: 1. half I -- 2. half II
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Chem. Soc. 2002,124, 1039610415. Chapter 1. 2 33 Rearrangements Claisen and Related Rearrangements David R. Williams and Partha P. ' The ally1 vinyl ether structural motif 1 smoothly undergoes reorganization to the y,& unsaturated carbonyl compound 2 under thermal or acid-catalyzed conditions. The [3,3]-sigmatropic reaction is a symmetry-allowed pericyclic process which proceeds via the six-membered closed transition state. 2 has been devoted to determine the rate accelerating effect of solvents and substituents at C1, C d and c6 which suggest the existence of a radical (6) or dipolar nature (7) of the transition statea3 Gajewski has described labelling studies that suggests the bond breaking event may proceed prior to the bond making event thereby reinforcing the concept of radical character in an asynchronous reaction p r ~ f i l e .
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