Mechanistic Study on the Ruthenium-Catalyzed Direct Amination of Alcohols
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https://figshare.com/articles/dataset/Mechanistic_Study_on_the_Ruthenium_Catalyzed_Direct_Amination_of_Alcohols/2306305
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资源简介：
The
Ru-catalyzed direct amination of alcohols with ammonia was
investigated for the RuHCl(CO)(PPh3)3/Xantphos
system in order to gain mechanistic insight. For several Ru(II) precursor
complexes the influence of different additives on catalytic performance
was investigated. NMR studies revealed that the reaction of RuHCl(CO)(PPh3)3/Xantphos with the alcohol in the presence of
a strong base initially formed an inactive dihydrido Ru species. However,
by addition of a ketone, the dihydride was (re)activated, where the
corresponding imine is the actual activator, formed by immediate condensation
of the ketone with ammonia. In the absence of a base, added ketone
significantly enhanced catalyst activity. Catalytically inactive RuCl2(PPh3)3 could be activated by base,
demonstrating that also complexes without the CO ligand give active
catalysts. On the basis of these observations a mechanism was proposed,
closely related to known transfer hydrogenation mechanisms.
创建时间：
2016-02-17
