Nucleophilic acyl substitutions of anhydrides with protic nucleophiles catalyzed by amphoteric, oxomolybdenum species.
[reaction: see text] 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-MoO(2)Cl(2) adduct with a given functional alkanoic acid, one can achieve oleate, dipeptide, diphenylmethyl, N-Fmoc-alpha-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-MoOCl(2)(O(2)CBu(t)())(2) between pivalic anhydride and MoO(2)Cl(2) as the catalyst.
Chen
Chien-Tien
CT
Department of Chemistry, National Taiwan Normal University, Taipei 11650, Taiwan. chefv043@scc.ntnu.edu.tw
Kuo
Jen-Huang
JH
Pawar
Vijay D
VD
Munot
Yogesh S
YS
Weng
Shieu-Shien
SS
Ku
Cheng-Hsiu
CH
Liu
Cheng-Yuan
CY