The synthesis of per-C-deuterated D-glucose11Presented at the 2nd Joint CIC-ACS Conference, Montreal, Quebec, Canada, June 1, 1977.

Stereo‐ and Regioselective Direct Multi‐Deuterium‐Labeling Methods for Sugars

“…[10,11] Deuterium-labeled sugars are also powerful chiral building blocks [12] to synthesize the new and useful chiral deuterated precursors of bioactive molecules. [17] On the other hand, we have recently developed the efficient and direct H-D exchange reaction of various organic substrates in the presence of an activated carbon-supported platinum group catalyst (Pd/C, Pt/C, Rh/C) under a hydrogen atmosphere in D 2 O as a cheap deuterium source. Meanwhile, direct deuteration methods of sugars have been achieved by using Raney Ni as a catalyst in D 2 O under a hydrogen atmosphere, although this method is not so efficient in terms of the necessity of microwave or ultrasonic assists and relatively low deuterium efficiencies.…”

“…Meanwhile, direct deuteration methods of sugars have been achieved by using Raney Ni as a catalyst in D 2 O under a hydrogen atmosphere, although this method is not so efficient in terms of the necessity of microwave or ultrasonic assists and relatively low deuterium efficiencies. [17] On the other hand, we have recently developed the efficient and direct H-D exchange reaction of various organic substrates in the presence of an activated carbon-supported platinum group catalyst (Pd/C, Pt/C, Rh/C) under a hydrogen atmosphere in D 2 O as a cheap deuterium source. [2,18] During the course of our study, ruthenium on carbon (Ru/ C) was found to efficiently catalyze the deuterium incorporation on the carbons adjacent to the free hydroxyl groups (a postions) under H 2 /D 2 O conditions (Scheme 1), [19] whereas the Ru/C-catalyzed H-D exchange reaction never proceeded at the a-position of the protected-hydroxy groups, such as the acetoxy and methoxy groups.…”

New Gateways to the Platinum Group Metal-Catalyzed Direct Deuterium-Labeling Method Utilizing Hydrogen as a Catalyst Activator

“…Although the deuteration of sugar derivatives using Raney Ni in D 2 O was previously reported, the deuterium efficiency is unsatisfactory and harsh reaction conditions using ultrasonication or microwaves are required. [24][25][26][27][28][29][30][31][32] In contrast, the present method under milder reaction conditions with a wide scope of substrates is useful and valuable to synthesize various types of deuterium-labeled sugars. 33,34) Encouraged by the novel aspect of the proposed reaction mechanisms for the H-D exchange reaction of alcohols (Section 2, Chart 5), we have focused on the development of dehydrogenative oxidation of alcohols into carbonyl products.…”

Nickel‐catalyzed hydrogen isotope exchange

“…Refluxing of a THF solution of diphenylmethane with ‘deuterated’ Raney nickel gave diphenyl[D 2 ]methane 9. ‘Deuterated’ Raney nickel is prepared10 by extensive washing of standard Raney nickel (prepared with non‐isotopic water and base) with deuterium oxide. It is distinguished from ‘deuterated Raney nickel’ whose preparation, detailed below, involves isotopic reagents for its preparation.…”

“…In their synthesis of perdeutero D‐glucose, Koch and Stuart10 used Raney nickel‐catalyzed deuteration (‘deuterated’ Raney nickel, D 2 O, reflux, 15 h) at two stages to install most of the labels. As illustrated in Figure 5, 1,2‐ O ‐isopropylidene‐ α ‐ D ‐[1‐D]glucofuranose ( I ) so treated gave the corresponding [1,5,6,6‐D 4 ]‐isotopolog (along with its C5‐epimer), and methyl α ‐ D ‐[1,5,6,6‐D 4 ]glucopyranoside ( II ) its perdeuterated isotopolog.…”