A Water/Toluene Biphasic Medium Improves Yields and Deuterium Incorporation into Alcohols in the Transfer Hydrogenation of Aldehydes

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 D2O, as the only deuterium source. Different aromatic, alkylic and alpha,beta-unsaturated aldehydes were reduced in the presence of [RuCl(p-cymene)(dmbpy)]BF4, (dmbpy=4,4 '-dimethyl-2,2 '-bipyridine) as the pre-catalyst and HCO2Na/HCO2H 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 D2O/toluene). The deuteration took place due to an efficient effective M-H/D+ exchange from D2O that allows the inversion of polarity of D+ (umpolung). DFT calculations that explain the catalytic behavior in water are also included.

Automated summary

Deuterium labeling is a process that leads to compounds useful in various fields, with the transfer hydrogenation of aldehydes and selective deuteration of alcohols described in this study. The use of a biphasic water/toluene system was found to enable higher yields and selective D incorporation. Additionally, efficient M-H/D+ exchange from D2O was found to play a key role in the deuteration process.