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. 2021 Jan 28;11(9):5080-5085.
doi: 10.1039/d0ra09437d. eCollection 2021 Jan 25.

Mechanically induced solvent-free esterification method at room temperature

Lei Zheng  1 , Chen Sun  1 , Wenhao Xu  1   2 , Alexandr V Dushkin  3 , Nikolay Polyakov  3 , Weike Su  1   2 , Jingbo Yu  2
Affiliations

Mechanically induced solvent-free esterification method at room temperature

Lei Zheng et al. RSC Adv. .

Abstract

Herein, we describe two novel strategies for the synthesis of esters, as achieved under high-speed ball-milling (HSBM) conditions at room temperature. In the presence of I2 and KH2PO2, the reactions afford the desired esterification derivatives in 45% to 91% yields within 20 min of grinding. Meanwhile, using KI and P(OEt)3, esterification products can be obtained in 24% to 85% yields after 60 min of grinding. In addition, the I2/KH2PO2 protocol was successfully extended to the late-stage diversification of natural products showing the robustness of this useful approach. Further application of this method in the synthesis of inositol nicotinate was also discussed.

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Conflict of interest statement

There are no conflicts to declare.

Figures

Scheme 1
Scheme 1. Mechanically induced synthetic of derivatives containing an ester group. (a) Buchwald's work; (b) Robles's work; (c) Szostak's work; (d) Lee's work; (e) this work; (f) mechanosynthesis of inositol nicotinate.
Fig. 1
Fig. 1. Influence of milling time and frequency on the reaction. (a) Path a; (b) path b.
Scheme 2
Scheme 2. Mechanosynthesis of inositol nicotinate.
Scheme 3
Scheme 3. Control experiments. (a) Mechanistic study of KI/P(OEt)3 strategy; (b) mechanistic study of I2/KH2PO2 strategy; (c) the synthesis of N-benzamide; (d) the sythesis of S-(m-tolyl) benzothioate; (e) the capture of possible intermediates in the I2/KH2PO2 strategy; (f) verification of radical mechanism; (g) reaction kinetics.
Scheme 4
Scheme 4. Plausible reaction mechanism: (a) path A; (b) path B.
See this image and copyright information in PMC

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