Visible-Light-Mediated Intramolecular Lactonization of Benzylic C(sp³)–H Bonds Promoted by DDQ and tert-Butyl Nitrite

Abstract

A functionalization of benzylic C(sp³)–H bonds was established through a mild metal-free intramolecular lactonization protocol in the presence of DDQ/tert-butyl nitrite as photocatalysts, allowing practical and low-cost access to a series of phthalide products in moderate to excellent yields. Compared with many existing methodologies, this visible-light-driven process exhibits an excellent substrate scope and fascinating features, including the formation of water as the sole byproduct, an abundant and green energy source, commercially available catalysts, and room-temperature reaction. Finally, detailed mechanistic investigations clearly revealed the role of the photocatalysts and molecular oxygen.

Key words

photocatalysis - lactonization - phthalides - benzylbenzoic acids

Publication History

Received: 11 August 2023

Accepted after revision: 04 October 2023

Accepted Manuscript online:
04 October 2023

Article published online:
03 November 2023

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• 15 Phthalides 2a–ac; General Procedure A Schlenk tube was charged with MeCN (3 mL), and the appropriate substrate 1 (0.5 mmol), DDQ (20 mol%), and 5 Å MS (50 mg) were added. The tube was flushed with O₂ then TBN (20 mol%, 12 μL) was quickly injected into the tube from a microsyringe, and the tube was then capped. The mixture was stirred for 0.5 h and then the tube was placed a dark box and illuminated with a blue LED (450–455 nm) at rt for 12 h. When the reaction was completed (GC), the light source device was removed. The resulting mixture was concentrated on a rotary evaporator, and the residue was purified by column chromatography (silica gel, PE–EtOAc). 3-Phenyl-2-benzofuran-1(3H)-one (2a) White solid; mp 120–121 °C. ¹H NMR (400 MHz, CDCl₃, TMS): δ = 7.96 (d, J = 7.6 Hz, 1 H), 7.67–7.62 (m, 1 H), 7.58–7.52 (m, 1 H), 7.40–7.35 (m, 3 H), 7.33 (d, J = 7.6 Hz, 1 H), 7.30–7.25 (m, 2 H), 6.40 (s, 1 H). ¹³C NMR (100 MHz, CDCl₃, TMS): δ = 170.6, 149.8, 136.5, 134.4, 129.5, 129.4, 129.1, 127.1, 125.7, 125.6, 123.0, 82.8. MS (EI): m/z (%) 210.23 [M⁺] (40), 104.11 (100).