Visible-Light-Driven Phosphonoalkylation of Alkenes

Abstract

Phosphonylation of alkenes is important for the generation of valuable organophosphines. However, redox-neutral difunctionalization of alkenes with readily available H-P(O) compounds remains underdeveloped. Herein, we report the first visible-light-driven redox-neutral phosphonoalkylation of alkenes. A variety of organophosphorus-containing three-membered carbocyclic scaffolds are synthesized from alkene-bearing alkyl sulfonates with H-P(O) compounds. The transition-metal-free protocol displays good functional group tolerance, broad substrate scope, high yields, and mild reaction conditions.

Key words

visible light - redox-neutral - difunctionalization of alkene - cyclopropane - organophosphine

Publication History

Received: 30 October 2020

Accepted after revision: 23 December 2020

Article published online:
12 February 2021

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• 14 Synthesis of 3aa: An oven-dried Schlenk tube (10 mL) containing a stirring bar was charged with 1a (0.2 mmol) and 4CzIPN (0.004 mmol, 3.2 mg, 2 mol%). Subsequently, the Schlenk tube was introduced in a glovebox, where it was charged with Cs₂CO₃ (0.3 mmol, 97.5 mg, 1.5 equiv) and HP(O)Ph₂ (2a). The tube was taken out of the glovebox and connected to a vacuum line where it was evacuated and back-filled with N₂ three times. DMF (2 mL) was then added under N₂ flow and the reaction mixture was sealed in the tube and placed at a distance of 2–4 cm from a 30 W blue LED and stirred at room temperature (25 °C) for 1.5 h. The reaction was then quenched with H₂O (1 mL), and the mixture was extracted with EtOAc and concentrated in vacuo. The residue was purified by silica gel flash chromatography (0.05% AcOH in petroleum ether/EtOAc = 1:1) to give the corresponding desired product 3aa (89.7 mg, 92%). ¹H NMR (400 MHz, CDCl₃): δ = 7.63–7.50 (m, 4 H), 7.46–7.39 (m, 4 H), 7.35 (m, 3 H), 7.28 (m, 4 H), 7.24–7.15 (m, 4 H), 2.74 (d, J = 10.2 Hz, 2 H), 1.16–1.05 (m, 2 H), 0.95 (q, J = 2.2 Hz, 2 H). ¹³C NMR (101 MHz, CDCl₃): δ = 143.06 (d, J = 2.3 Hz), 141.05, 139.04, 133.55 (d, J = 97.3 Hz), 131.04 (d, J = 2.8 Hz), 130.53 (d, J = 9.2 Hz), 129.78, 128.63, 128.23 (d, J = 11.5 Hz), 126.98, 126.93, 126.62, 40.43 (d, J = 71.1 Hz), 20.51 (d, J = 4.6 Hz), 13.33 (d, J = 7.2 Hz). ³¹P NMR (162 MHz, CDCl₃): δ = 28.78. HRMS: m/z [M + Na]⁺ calcd for C₂₈H₂₅OP: 431.1535; found: 431.1532.