On intramolecular dyotropy: Structural effects on reaction rates and x-ray crystal structure - molecular mechanics correlations

✍ Scribed by Judith A.K. Howard; Kenneth Mackenzie; Robert E. Johnson; K.Brian Astin

• Publisher: Elsevier Science
• Year: 1989
• Tongue: French
• Weight: 302 KB
• Volume: 30
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(01)80567-0

✦ Synopsis

Differential kinetic behaviour in thermal dyotropic rearrangement of compounds containing a cyclohexa-1,3-diene ring as 2H donor held proximate to a variously-substituted norbomene element as acceptor is discussed in terms of parameters derived by single crystal X-ray structure analysis and Molecular Mechanics calculations. Contemporary interest1p2 in the stereospecific intra-molecular group-transfer of two hydrogen atoms to a proximate x-bond in a non-catalysed thermal dyotropic rearrangement? prompts us to report further examples of this process in appropriate model compounds [L, 2 and 2 below] and to comment on structural effects on rearrangement rates for these and analogous compounds we have previously described.3

Zn/Cu-couple reduction of isodrin2 (Et20r 36") gives convenient high-yield access to m and Full details will appear later with the X-ray results for 2.