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A Water/Toluene Biphasic Medium Improves Yields and Deuterium Incorporation into Alcohols in the Transfer Hydrogenation of Aldehydes
Author(s) -
RuizCastañeda Margarita,
Santos Lucía,
Manzano Blanca R.,
Espino Gustavo,
Jalón Félix A.
Publication year - 2021
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.202100022
Subject(s) - chemistry , toluene , deuterium , furfuryl alcohol , catalysis , furfural , alcohol , methylcyclohexane , hydrogen , triflic acid , organic chemistry , transfer hydrogenation , umpolung , medicinal chemistry , physics , quantum mechanics , ruthenium , nucleophile
Abstract Deuterium labeling is an interesting process that leads to compounds of use in different fields. We describe the transfer hydrogenation of aldehydes and the selective C 1 deuteration of the obtained alcohols in D 2 O, as the only deuterium source. Different aromatic, alkylic and α,β‐unsaturated aldehydes were reduced in the presence of [RuCl(p‐cymene)(dmbpy)]BF 4 , (dmbpy=4,4′‐dimethyl‐2,2′‐bipyridine) as the pre‐catalyst and HCO 2 Na/HCO 2 H as the hydrogen source. Moreover, furfural and glucose, were selectively reduced to the valuable alcohols, furfuryl alcohol and sorbitol. The processes were carried out in neat water or in a biphasic water/toluene system. The biphasic system allowed easy recycling, higher yields, and higher selective D incorporation (using D 2 O/toluene). The deuteration took place due to an efficient effective M–H/D + exchange from D 2 O that allows the inversion of polarity of D + (umpolung). DFT calculations that explain the catalytic behavior in water are also included.