American Chemical Society
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Nucleophilic Acyl Substitutions of Anhydrides with Protic Nucleophiles Catalyzed by Amphoteric, Oxomolybdenum Species

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journal contribution
posted on 2005-02-18, 00:00 authored by Chien-Tien Chen, Jen-Huang Kuo, Vijay D. Pawar, Yogesh S. Munot, Shieu-Shien Weng, Cheng-Hsiu Ku, Cheng-Yuan Liu
Among six different group VIb oxometallic species examined, dioxomolybdenum dichloride and oxomolybdenum tetrachloride were the most efficient catalysts to facilitate nucleophilic acyl substitution (NAS) of anhydrides with a myriad array of alcohols, amines, and thiols in high yields and high chemoselectivity. In contrast to the well-recognized redox chemical behaviors associated with oxomolybdenum(VI) species, the catalytic NAS was unprecedented and tolerates virtually all kinds of functional groups. By using benzoic anhydride as a mediator for in situ generation of an incipient mixed anhydride−MoO2Cl2 adduct with a given functional alkanoic acid, one can achieve oleate, dipeptide, diphenylmethyl, N-Fmoc-α-amino, pyruvic, and tert-butylthio ester, N-tert-butylamide, and trityl methacrylate syntheses with appropriate protic nucleophiles. The amphoteric character of the MoO unit in oxomolybdenum chlorides was found to be responsible for the catalytic NAS profile as supported by a control NAS reaction of using an authentic adduct−MoOCl2(O2CBut)2 between pivalic anhydride and MoO2Cl2 as the catalyst.