Photoinduced Regioselective Lactonization of ortho-Iodobenzoic Acids with Alkenes: Synthesis of 3,4-Dihydroisocoumarin Derivatives

Abstract

A photoinduced strategy for the synthesis of a variety of 3,4-dihydroisocoumarins has been realized. The reactions proceeded from ortho-iodobenzoic acids and alkenes through a photodehalogenative lactonization with NaHCO₃ as the only additive in dimethyl sulfoxide (DMSO) to provide the desired products in moderate to good yields. This method offers a simple, mild, and environmentally friendly route to 3,4-dihydroisocoumarin derivatives.

Key words

3,4-dihydroisocoumarin - o-iodobenzoic acids - alkenes - radical lactonization - difunctionalization

• References and Notes

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• 13 A mixture of 2-iodo-5-methylbenzoic acid (2a; 0.2 mmol, 1 equiv), styrene 1a (0.8 mmol, 4 equiv) and NaHCO₃ (0.26 mmol, 1.3 equiv) in DMSO (4 mL) was put into a quartz reaction tube (10 mL). N₂ was flowed in for 10 min, then the tube was sealed and exposed to illumination with a high-pressure mercury lamp at 300 nm wavelength for 6 h. Water (20 mL) was added to the reaction system and the mixture was extracted with ethyl acetate (3 × 20 mL). The organic phase was washed with saturated salt water, dried with anhydrous sodium sulfate, and the crude products were obtained under reduced pressure and concentration. The purified products were purified by silica gel column chromatography (PE/EtOAc, 10:1), and the product 7-methyl-3-phenylisochroman-1-one 3a (75%) was obtained as a pale-yellow liquid. ¹H NMR (400 MHz, CDCl₃): δ = 7.97 (s, 1 H), 7.52–7.33 (m, 6 H), 7.17 (d, J = 7.7 Hz, 1 H), 5.53 (dd, J = 12.0, 3.2 Hz, 1 H), 3.29 (dd, J = 16.3, 12.0 Hz, 1 H), 3.10 (dd, J = 16.4, 3.2 Hz, 1 H), 2.41 (s, 3 H). ¹³C NMR (151 MHz, CDCl₃): δ = 165.6, 138.6, 137.7, 135.0, 134.8, 130.6, 128.6, 128.6, 127.2, 126.1, 124.8, 80.0, 35.2, 21.0. HRMS (ESI): m/z [M + H]⁺ calcd for C₁₆H₁₅O₂: 239.1067; found: 239.1066.