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Ruthenium‐Catalyzed Regioselective Deuteration of Alcohols at the β‐Carbon Position with Deuterium Oxide
Author(s) -
Tse Sunny Kai San,
Xue Peng,
Lau Christy Wai Sum,
Sung Herman H. Y.,
Williams Ian D.,
Jia Guochen
Publication year - 2011
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201101542
Subject(s) - chemistry , ruthenium , ethanolamine , catalysis , regioselectivity , medicinal chemistry , deuterium , enol , organic chemistry , photochemistry , physics , quantum mechanics
A convenient method for regioselective H/D exchange between D 2 O and alcohols at the β‐carbon position using the catalytic system [( p ‐cymene)RuCl 2 ]/ethanolamine/KOH is described. This method is applicable for deuteration of both primary and secondary alcohols. The H/D exchange reactions proceed through an oxidation/modification/reduction reaction sequence. Alcohols are first temporarily oxidized to carbonyl compounds by the hydrogen transfer catalyst. The carbonyl compounds then undergo deuteration at the carbon adjacent to the carbonyl group by keto–enol tautomerization in the presence of D 2 O and a catalytic amount of base. The deuterated carbonyl compounds are then reduced to produce deuterated alcohols. In support of the reaction mechanism, a well‐defined bimetallic ruthenium complex was isolated from the reaction of [{( p ‐cymene)RuCl 2 } 2 ] with ethanolamine. The activity of this complex is similar to that of [{( p ‐cymene)RuCl 2 } 2 ]/ethanolamine.