Mild Copper-Catalyzed Addition of Arylboronic Esters to Di-tert-butyl Dicarbonate: An Easy Access to Methyl Arylcarboxylates

Abstract

An efficient copper-catalyzed addition of arylboronic esters to (Boc)₂O was developed. The reaction can be conducted under exceedingly mild conditions and is compatible with a variety of synthetically relevant functional groups. It therefore represents a useful alternative route for the synthesis of methyl arylcarboxylates. A preliminary mechanistic study indicated the involvement of an addition–elimination mechanism.

Key words

copper catalysis - arylboronic esters - addition - carboxylation - methyl arylcarboxylates

Publication History

Received: 29 December 2020

Accepted after revision: 29 January 2021

Accepted Manuscript online:
29 January 2021

Article published online:
17 February 2021

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• 15 Methyl (Het)arylcarboxylates 3a–y, 5a–e; General Procedure A 15 mL Schlenk tube equipped with a stirrer bar was charged with CuCl (10 mol%), L7 (13 mol%), LiOMe (2.5 equiv), and the appropriate boronic ester 1 or 4 (0.375 mmol). The vessel was then evacuated and filled with Ar (three cycles). DMA (0.5 mL) and (Boc)₂O (0.25 mmol) were added sequentially under Ar, and the mixture was stirred at 30 ℃ for 6 h. MeI (5 equiv) was then added in air, and the mixture was stirred at 30 ℃ for additional 2 h. The mixture was finally diluted with EtOAc and washed with sat. aq NaCl (20 mL). The aqueous phase was further extracted with EtOAc (3 × 20 mL), and the combined organic phases were dried (Na₂SO₄) and concentrated. The residue was purified by column chromatography [silica gel EtOAc–hexane (1:100 to 1:50)]. Methyl 2-Naphthoate (3b) Prepared by following the general procedure as a white solid; yield: 91% (by HPLC). ¹H NMR (400 MHz, CDCl₃): δ = 8.62 (s, 1 H), 8.08–8.05 (m, 1 H), 7.96 (d, J = 8.0 Hz, 1 H), 7.88 (d, J = 8.7 Hz, 2 H), 7.63–7.49 (m, 2 H), 3.98 (s, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 167.29, 135.53, 132.51, 131.09, 129.37, 128.25, 128.17, 127.78, 127.41, 126.66, 125.24, 52.26. The NMR spectral data agreed with the reported values.¹⁶
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