2024-03-28T11:40:28Z
https://nagoya.repo.nii.ac.jp/oai
oai:nagoya.repo.nii.ac.jp:02001701
2023-01-16T05:08:39Z
320:321:322
Insight into the Mechanism of the Acylation of Alcohols with Acid Anhydrides Catalyzed by Phosphoric Acid Derivatives
Hayashi, Hiroyuki
Yasukochi, Shotaro
Sakamoto, Tatsuhiro
Hatano, Manabu
Ishihara, Kazuaki
open access
This document is the Accepted Manuscript version of a Published Work that appeared in final form in [The Journal of Organic Chemistry], copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see [https://pubs.acs.org/articlesonrequest/AOR-H4BMERSYU3X9TT2KYSWC].”
Insight into the mechanism of a safe, simple, and inexpensive phosphoric acid (H3PO4)-catalyzed acylation of alcohols with acid anhydrides is described. The corresponding in situ-generated diacylated mixed anhydrides, unlike traditionally proposed monoacylated mixed anhydrides, are proposed as the active species. In particular, the diacylated mixed anhydrides act as efficient catalytic acyl transfer reagents rather than as Brønsted acid catalysts simply activating acid anhydrides. Remarkably, highly efficient phosphoric acid (1–3 mol %)-catalyzed acylation of alcohols with acid anhydrides was achieved and a 23 g scale synthesis of an ester was demonstrated. Also, phosphoric acid catalyst was effective for synthetically useful esterification from carboxylic acids, alcohols, and acid anhydride. Moreover, with regard to recent developments in chiral 1,1′-bi-2-naphthol (BINOL)-derived phosphoric acid diester catalysts toward asymmetric kinetic resolution of alcohols by acylation, some phosphate diesters were examined. As a result, a 31P NMR study and a kinetics study strongly supported not only the acid–base cooperative mechanism as previously proposed by other researchers but also the mixed anhydride mechanism as presently proposed by us.
ACS Publications
2022-04-02
2021-04-02
eng
journal article
AM
http://hdl.handle.net/2237/0002001701
https://nagoya.repo.nii.ac.jp/records/2001701
https://doi.org/10.1021/acs.joc.1c00102
0022-3263
The Journal of Organic Chemistry
86
7
5197
5212
https://nagoya.repo.nii.ac.jp/record/2001701/files/JOC.pdf
application/pdf
2 MB
2022-04-02