Ruthenium-Catalyzed Deuteration of Alcohols with Deuterium Oxide

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• 作者：Wei Bai ; Ka-Ho Lee ; Sunny Kai San Tse ; Ka Wing Chan ; Zhenyang Lin ; Guochen Jia
• 刊名：Organometallics
• 出版年：2015
• 出版时间：August 10, 2015
• 年：2015
• 卷：34
• 期：15
• 页码：3686-3698
• 全文大小：759K
• ISSN：1520-6041

文摘

The catalytic properties of a series of ruthenium complexes for H/D exchange between D₂O and alcohols were studied. The catalytic activity of the ruthenium complexes and the regioselectivity of the H/D exchange reactions were found to be dependent on the auxiliary ligands. While ruthenium 畏⁶-cymene complexes such as [(畏⁶-cymene)RuCl(NH₂CH₂CH₂NTs)]Cl, (畏⁶-cymene)RuCl₂/NH₂CH₂CH₂OH, and (畏⁶-cymene)Ru{(S,S)-NHCHPhCHPhNTs} catalyzed regioselective deuteration of alcohols with D₂O at the 尾-carbon positions only, octahedral ruthenium complexes such as RuCl₂(2-NH₂CH₂Py)(PPh₃)₂ (2-NH₂CH₂Py = 2-aminomethylpyridine) and RuCl₂(NH₂CH₂CH₂NH₂)(PPh₃)₂ catalyzed regioselective H/D exchange reactions of D₂O with alcohols at both the 伪- and 尾-carbon positions of alcohols. The H/D exchange reactions proceed through reversible dehydrogenation of alcohols and hydrogenation of carbonyl compounds involving hydride species and H/D exchange among D₂O and carbonyl and hydride species. The different regioselectivities of the H/D exchange reactions can be related to the relative ease of H/D exchange of ruthenium hydride intermediates with D₂O.