Premium
Organocatalytic Aerobic Oxidation of α‐Fluoroalkyl Alcohols to Fluoroalkyl Ketones at Room Temperature
Author(s) -
Kadoh Yoichi,
Tashiro Masayuki,
Oisaki Kounosuke,
Kanai Motomu
Publication year - 2015
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201500131
Subject(s) - chemistry , ketone , trifluoromethyl , yield (engineering) , acetic acid , alcohol oxidation , aldehyde , organic chemistry , radical , functional group , fluorine , catalysis , oxide , oxygen , combinatorial chemistry , polymer , alkyl , materials science , metallurgy
The organocatalytic aerobic oxidation of electron‐deficient α‐fluoroalkyl alcohols at room temperature is described. The resulting fluoroalkyl ketones are versatile synthetic intermediates for a variety of fluorine‐containing molecules. This otherwise difficult transformation has now been accomplished by the reaction of α‐fluoroalkyl alcohols with N ‐oxyl radicals, catalytically generated from 9‐azabicyclo[3.3.1]nonan‐3‐one N ‐oxyl/nitrogen oxide (keto‐ABNO/NO x ) and oxygen in acetic acid (AcOH), affording the corresponding fluoroalkyl ketones in high yield. This operationally simple reaction can be performed under mild conditions, and was applied to a wide range of alcohols (20 examples), thus demonstrating a high functional group tolerance. Moreover, a modified one‐pot protocol based on this method was able to convert an aldehyde to a trifluoromethyl ketone on a gram scale.