Synlett 2019; 30(13): 1561-1564
DOI: 10.1055/s-0037-1611868
© Georg Thieme Verlag Stuttgart · New York

Chelation-Based Homologation by Reaction of Organometallic Reagents with O-Alkyl S-Pyridin-2-yl Thiocarbonates: Synthesis of Esters from Grignard Reagents

Shun Usami
Tomoyuki Suzuki
Koudai Mano
Kosaku Tanaka III
Yoshimitsu Hashimoto
Nobuyoshi Morita
Osamu Tamura
This work was supported by JSPSKAKENHI Grant Number 17K0821 (O.T.).
Further Information

Publication History

Received: 20 April 2019

Accepted after revision: 03 June 2019

Publication Date:
27 June 2019 (online)

This paper is dedicated to the memory of Professor Teruaki Mukaiyama, a prominent scientist who made major contributions to the field.


The one-carbon homologative esterification of Grignard reagents with O-alkyl S-pyridin-2-yl thiocarbonates has been explored. This one-step synthesis of esters from Grignard reagents is the first case to involve chelation-stabilized intermediates.

Supporting Information

  • References and Notes

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      A dry carbon dioxide equivalent of the Grignard reaction has recently been reported; see:
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  • 13 Benzyl Benzoate (4a); Typical Procedure A 1.0 M solution of PhMgBr (5a) in THF (98 mL, 98 mmol) was added to a stirred solution of 1 (24.1 mg, 98.2 μmol) in dry THF (1.0 mL) at 0 °C and the mixture was kept at 50 °C for 1 h, then cooled to 0 °C. An aqueous solution of NH4Cl was added, and the mixture was extracted with Et2O. The organic layer was washed with brine, dried (Na2SO4), and concentrated in vacuo. The residue purified by chromatography [silica gel, hexane–EtOAc (20:1)] to give 4a as an oil; yield: 17.5 mg (84%). 1H NMR (300 MHz, CDCl3): δ = 8.10–8.06 (m, 2H), 7.32–7.59 (m, 8 H), 5.37 (s, 2 H). This spectrum was identical with that reported.14
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