Kinetic, thermodynamic and mechanistic studies on the reduction of carbenium ions by NAD(P)H analogues

✍ Scribed by Jin-Pei Cheng; Yun Lu

• Publisher: John Wiley and Sons
• Year: 1997
• Tongue: English
• Weight: 177 KB
• Volume: 10
• Category: Article
• ISSN: 0894-3230
• DOI: 10.1002/(sici)1099-1395(199707)10:7<577::aid-poc920>3.0.co;2-t

✦ Synopsis

Hydride transfer mechanisms of the reductions of xanthylium ion by NAD(P)H analogues (i.e. BNAH, HEH and AcrH 2 ) were investigated. Both the kinetic observations and an analysis of thermodynamic driving forces for each mechanistic step in all the possible mechanisms indicate that the reductions are initiated by a rate-determining electron transfer, followed by a fast hydrogen atom abstraction. The mechanism of the reductions of 9-phenylxanthylium and triphenylmethylium ions by BNAH were also investigated and are similarly discussed.