Catalytic nucleophilic acyl substitution of anhydrides by amphoteric vanadyl triflate

Organic Letters

Volumn 3, Issue 23, 2001, Pages 3729-3732

  Chen, Chien Tien ^a   Chang, I Hsin ^a   Lin, Jin Sheng ^a   Liu, Chin Jing ^a   Chou, Y Chen ^a   Kuo, Jen Huang ^a   Li, Chun Hsin ^a   Barhate, N B ^a   Hon, Sang Wen ^a   Li, Tai Wei ^a   Chao, Shi Deh ^a   Liu, Chia Cheng ^a   Li, Ying Chieh ^a  

^a NATIONAL TAIWAN NORMAL UNIVERSITY   (Taiwan)

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ARTICLE;

EID: 18044401091     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol016684c     Document Type: Article

References (34)

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23. See Supporting Information.
24. 3 is moisture-sensitive but was found to be catalytically active (100% yield, 1.5 h).
25. A mixture of products was obtained under usual conditions (acid chloride/pyridine). For its effective acetylation mediated by TMSOTf, lower reaction temperature (-10°C in ethyl acetate) was required (ref 5).
26. Conventional procedure (acid chloride/pyridine) led to only pinacol rearrangement product.
27. 2-mediated acetylation.
28. (b) Ishii, Y.; Takeno, M.; Kawasaki. Y.; Muromachi, A.: Nishiyama, Y.; Sakaguchi, S. J. Org. Chem. 1996, 61, 3088.
29. Pivalations did not work properly because of the poor solubility of these substrates in pivalic anhydride.
30. (a) Further stirring with excess of acetic and pivalic anhydride (10 equiv) for another 18 and 72 h (50°C) furnished the corresponding diacetylated and dipivalated products in 87% and 89% yields, respectively.
31. (b) In DMAP catalyzed acylation in pyridine, reversed chem-selectivity was observed in this case as a result of the more acidic nature of phenolic OH.
32. By using the pivalic anhydride/pyridine protocol, the desired product was isolated in only 20% yield.
33. It was found that amines, thiols, and primary and aromatic alcohols are amenable to benzoylations. Benzoylations of secondary alcohols are rather limited and require harsher reaction conditions. So far, the only workable substrate is as shown in entry 1, Table 3, which underwent benzoylation at 50°C in 52% yield.
34. For an elegant survey of other water-tolerant metal salts, see: Kobayashi, S.; Nagayama, S.; Busujima, T. J. Am. Chem. Soc. 1998, 120, 8287.