Origin of the preference for the chair conformation in the Cope rearrangement. Effect of phenyl substituents on the chair and boat transition states

…, GJ Stoddard, WP England, CD Haffner

文献索引：Shea; Stoddard; England; Haffner Journal of the American Chemical Society, 1992 , vol. 114, # 7 p. 2635 - 2643

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被引用次数: 17

摘要

Abstract: d, l-and meso-2, 2'-bis [l-methylene-l, 2, 3, 4-tetrahydronaphthalenes] 8 and 9 were synthesized, and the activation energy parameters for their unimolecular [3, 3] sigmatropic rearrangement to 1, 2-bis (3, 4-dihydro-l-naphthalenyl) ethane (13) were determined. The d, l diastereomer is constrained to undergo Cope rearrangement in the chair conformation while the meso diastereomer is constrained to the boat. At 150 OC kd,,/k,,= 7 X IO6. A ...