Deuteration of ketones through enamines

✍ Scribed by John P. Schaefer; David S. Weinberg

• Publisher: Elsevier Science
• Year: 1965
• Tongue: French
• Weight: 157 KB
• Volume: 6
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(00)90131-x

✦ Synopsis

Methods for deuterating orpjanic rsolecules have becceba increasinkly important in recentyearsbecause of the existing interest inmechanistic aspects of organic reactions, includin~decipberingofmassspectrsliragmentatlon p&terns. The susceptibility of ensminestoelectrophllicattack(1) suggested that these coaxpow& might be useful intermediates for the general aad stereospeclfic introduction of dauterium into ketones by selective hydrolysis in deuterated solvents. Reactionof phosphorus oxychloridewithdeuteri~oxide produced an aqueous solution of deuteriophosphoric acid cad deuterlochlorlc acid which waa covered with pentane and cooled to O". Addition of a solution of enauine inpentenewith stlrrinS resulted inrapldhydrolysis of the Elaine, extra&Ion of the ketone into the hydrocarbon phase, and retention of the amine as its salt in the aqueous phase; a ten-fold mobr excess of totalacidwaaemployed. Utilizing thisprocedure,gwre 2-deuterlocycl.ohexanonewas prepared inhighyieldf~l-morpholinocyclohenae a.

Deuterolysis of &-t-butyl-l-mnpholinocnocycloherene produced 2-S-deuterio-k-t-butylcrC lohexauone as would be predicted on stereoelectronic grounds (2);