Insight into the Mechanism of the Acylation of Alcohols with Acid Anhydrides Catalyzed by Phosphoric Acid Derivatives

Hiroyuki Hayashi, Shotaro Yasukochi, Tatsuhiro Sakamoto, Manabu Hatano* and Kazuaki Ishihara*

*Kobe Pharmaceutical University, Kobe 658-8558; Nagoya University, Nagoya 464-8603, Japan, Email: mhatanokobepharma-u.ac.jp, ishiharacc.nagoya-u.ac.jp

H. Hayashi, S. Yasukochi, T. Sakamoto, M. Hatano, K. Ishihara, J. Org. Chem., 2021, 86, 5197-5212.

DOI: 10.1021/acs.joc.1c00102

---

see article for more reactions

Abstract

Inexpensive phosphoric acid (H₃PO₄) catalyzes a safe and simple acylation of alcohols with acid anhydrides. In situ-generated diacylated mixed anhydrides are proposed as the active species - acting as efficient catalytic acyl transfer reagents. A 23 g scale synthesis of an ester was demonstrated.

see article for more examples

proposed mechanism

---

---

Key Words

acylation, acetic acid esters, pivalic acid esters

---

ID: J42-Y2021