Photoinduced Direct Carbamoylation of Ethers with Isocyanates towards the Synthesis of α-Amide-Substituted Ether Derivatives

Abstract

Photoinduced carbamoylation of ethers using isocyanates as amide sources was accomplished under mild and environmentally friendly reaction conditions. A series of isocyanates were tolerated in this protocol to construct α-amide-substituted ether derivatives with desired yields. The method featured broad substrate scope and good functional group tolerance, which could play an important role in the construction of biological molecules with ethers.

Keywords

carbamoylation - amides - photoinduced - isocyanates - C–H functionalization

Publication History

Received: 04 December 2023

Accepted after revision: 20 February 2024

Accepted Manuscript online:
20 February 2024

Article published online:
11 March 2024

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• 53 General Procedure for the Carbamoylation of Ethers with Isocyanate 1a A Schlenk tube was equipped with a magnetic stir bar and charged with isocyanate 1a (0.2 mmol, 1.0 equiv), tetrahydrofuran (1 mL), FeCl₃ (5 mol%), and DTBP (2 equiv). The resulting mixture was sealed and degassed via vacuum evacuation and back-filled with nitrogen for three times after freezing using liquid nitrogen, and then irradiated with a 20 W 390 nm LED at room temperature for 24 h. After the reaction ended, the reaction solution was concentrated in vacuo and purified by silica gel column chromatography to give the desired product 3a with yield of 81%. ¹H NMR (400 MHz, CDCl₃): δ = 8.34 (s, 1 H), 7.38 (d, J = 8.3 Hz, 2 H), 7.05 (d, J = 8.1 Hz, 2 H), 4.38 (dd, J = 8.2, 6.0 Hz, 1 H), 4.06–3.74 (m, 2 H), 2.34–2.25 (m, 1 H), 2.24 (s, 3 H), 2.10 (td, J = 13.2, 6.3 Hz, 1 H), 1.94–1.77 (m, 2 H). ¹³C NMR (101 MHz, CDCl₃): δ = 170.14, 133.71, 132.96, 128.47, 118.64, 77.62, 68.62, 29.17, 24.57, 19.85.