Catalytic Nucleophilic Acyl Substitution of Anhydrides by Amphoteric Vanadyl Triflate
Chien-Tien Chen*, Jen-Huang Kuo, Chun-Hsin Li, N. B. Barhate, Sang-Wen Hon, Tai-Wei Li, Shi-Deh Chao, Chia-Cheng Liu, Ying-Chieh Li, I-Hsin Chang, Jin-Sheng Lin, Chin-Jing Liu, and Y-Chen Chou
*Department of Chemistry, National Taiwan Normal University, Taipei, Taiwan, R.O.C.
Email: ctchenmx.nthu.edu.tw
C.-T. Chen, J.-H. Kuo, C.-H. Li, N. B. Barhate, S.-W. Hon, T.-W. Li, S.-D. Chao, C.-C. Liu, Y.-C. Li, I.-H. Chang, J.-S. Lin, C.-J. Liu, Y.-C. Chou, Org. Lett., 2001, 3, 3729-3732.
DOI: 10.1021/ol016684c
see article for more reactions
Abstract
Vanadyl triflate efficiently catalyzes a nucleophilic acyl substitution of anhydrides with a myriad array of alcohols, amines, and thiols in high yields and high chemoselectivity. By using mixed-anhydride technique, oleate and peptide syntheses can be achieved.
see article for more examples
Details
The study explores the catalytic efficiency of vanadyl triflate in nucleophilic acyl substitution of anhydrides with alcohols, amines, and thiols. Among four vanadyl species tested, vanadyl triflate emerged as the most effective catalyst, achieving high yields and chemoselectivity. The amphoteric nature of the V=O unit in vanadyl triflate is key to its catalytic performance, facilitating a stepwise, push-pull mechanism. The catalyst is compatible with various anhydrides, including acyclic, cyclic, aliphatic, and aromatic types, and can be reused multiple times without loss of activity. The protocol is tolerant to functional groups and allows for chemoselective acylation. Additionally, the mixed-anhydride technique enables acylations with commercially unavailable anhydrides, useful in oleate and peptide syntheses. The study highlights the potential of vanadyl triflate as a mild, neutral, and water-tolerant catalyst for diverse acylation reactions, offering a valuable tool for organic synthesis. Further investigations are ongoing to explore its applications in solution and solid-state peptide syntheses.
Key Words
acetates, pivalates, acylation
ID: J54-Y2001