Insight into the Mechanism of the Acylation of Alcohols with Acid Anhydrides Catalyzed by Phosphoric Acid Derivatives
Insight into the Mechanism of the Acylation of Alcohols with Acid Anhydrides Catalyzed by Phosphoric Acid Derivatives
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深入探讨磷酸衍生物催化醇与酸酐酰化的机理
DOI：
10.1021/acs.joc.1c00102
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发表时间：
2021
期刊：
影响因子：
--
通讯作者：
Ishihara Kazuaki
中科院分区：
文献类型：
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作者：
Hayashi Hiroyuki;Yasukochi Shotaro;Sakamoto Tatsuhiro;Hatano Manabu;Ishihara Kazuaki
深入了解一个安全，简单，廉价的磷酸（H3 PO 4）催化的醇与酸酐的酰化反应的机理。与传统的单酰化混合酸酐不同，相应的原位生成的双酰化混合酸酐被提议为活性物种。特别地，双酰化混合酸酐充当有效的催化酰基转移试剂，而不是简单地活化酸酐的布朗斯台德酸催化剂。值得注意的是，实现了醇与酸酐的高效磷酸（1- 3mol%）催化的酰化，并且证明了酯的23 g规模合成。此外，磷酸催化剂是有效的合成有用的酯化从羧酸，醇和酸酐。此外，关于手性1，1 ′-联-2-萘酚（BINOL）衍生的磷酸二酯催化剂用于通过酰化进行醇的不对称动力学拆分的最新进展，对一些磷酸二酯进行了研究。结果表明，~（31）P NMR研究和动力学研究不仅有力地支持了前人提出的酸碱协同反应机理，而且也支持了我们目前提出的混合酸酐反应机理。
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, a31P 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.