- Insights into the Molecular Recognition Process in Organocatalytic Chemoselective Monoacylation of 1,5-Pentanediol
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Monoacylation of long-chain linear diols often encounters difficulties associated with unavoidable overacylation affording the diacylate. However, several C1- and C2-symmetrical pyrrolidinopyridine (PPY) catalysts were found to effectively promote the chemoselective monoacylation of 1,5-pentanediol. The effects of catalyst structure on the performance for the monoacylation were investigated. The amide carbonyl group(s) in the pyrrolidine ring in both C1- and C2-symmetrical catalysts was(were) suggested to play the key role in selective monoacylation. On the other hand, the indolyl NH group in the amide side chain of the catalysts was found to be critically important for further increasing the chemoselectivity of monoacylation only when the catalyst has a C2-symmetrical structure. The effects of the catalyst structure on the chemoselective monoacylation were elucidated by DFT calculations, and the origin of the precise molecular recognition for 1,5-pentanediol by the catalysts and transition state (TS) stabilization effects by these functionalities were disclosed.
- Imayoshi, Ayumi,Yamanaka, Masahiro,Sato, Makoto,Yoshida, Keisuke,Furuta, Takumi,Ueda, Yoshihiro,Kawabata, Takeo
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supporting information
p. 1337 - 1344
(2016/04/26)
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- Organocatalytic chemoselective monoacylation of 1,n-linear diols
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Matters of length: Exclusive or predominant monoacylation of 1,n-linear diols took place in the presence of 1 when the chain length of linear diols was equal to or shorter than five carbon atoms. The chemoselectivity of acylation between 1,5-pentanediol (n=5) and 1,6-hexanediol (n=6) was 5.2, and that between 1,5-pentanediol and its monoacylate was 113. Copyright
- Yoshida, Keisuke,Furuta, Takumi,Kawabata, Takeo
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supporting information; experimental part
p. 4888 - 4892
(2011/06/22)
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