An electronic interpretation of the stereochemistry of the reduction of cyclohexanones

✍ Scribed by J. Klein

• Book ID: 104238538
• Publisher: Elsevier Science
• Year: 1973
• Tongue: French
• Weight: 236 KB
• Volume: 14
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(01)87206-3

✦ Synopsis

An WriCal rule forthe 8teX'eOChemiBtrg of the reduction of cyclohexanonea by complex hydrides vas first pronoun-by B@Mon".

Thi8 rule stated that reduction of unhindared cyclohemones gave predominantly equatorial, and that of hindered ones -axial almhol~.

Slnceitwaeknown that the e+atofiti W~ohexamle wer-s *e more stable ieomers, the preceding rule vae recast by Dauben and Soy-2) in another fom wb.ich aaid that the steric couree of the reduction of unhindered cyclohevanones vae determined by product developent control and that of hindered ketones by eteric approach control. It uaa clear, bowever, that the equatorial cyclohexanols were not formed by equilibration of the iaonerfc alcohole, but went kinetically formed products. The reason for their preferential formation va8 given in terms of steric hindrance 3.4) to approach framthe equatorial sidebythe axial hydrogen6 at the 2 and 6 poeitione of the ketones.