Borates as a Traceless Activation Group for Intermolecular Alkylarylation of Ethylene through Photoredox/Nickel Dual Catalysis

Xiaoliang Feng; Lei Guo; Shengqing Zhu; Lingling Chu

doi:10.1055/a-1320-6946

Synlett, Table of Contents

Synlett 2021; 32(15): 1519-1524
DOI: 10.1055/a-1320-6946

cluster

Modern Nickel-Catalyzed Reactions

Borates as a Traceless Activation Group for Intermolecular Alkylarylation of Ethylene through Photoredox/Nickel Dual Catalysis

Xiaoliang Feng

,

Lei Guo

,

Shengqing Zhu∗

,

Lingling Chu ∗

Abstract

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Abstract

A formal ethylene alkylarylation reaction with aryl halides and alkyl oxalates enabled by synergistic photoredox/nickel catalysis is reported. This protocol takes advantage of borates as a traceless activation group, achieving the formal ethylene difunctionalized products via a catalytic three-component 1,2-alkylarylation of vinyl borate followed by a base-assisted deborylation process. The mild conditions allow for excellent functional groups compatibility and broad substrate scope.

Key words

dicarbofunctionalization - vinyl borate - ethylene - nickel catalysis - synergistic catalysis

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References

References and Notes

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11 In a typical procedure, to a flame-dried 8 mL reaction vial was charged with NiCl₂·DME (0.02 mmol, 20 mol%), dtbbpy (0.02 mmol, 20 mol%), Ir[dF(CF₃)ppy]₂(dtbbpy)PF₆ (0.003 mmol, 3 mol%), 4-bromopyridine (2a, 0.1 mmol, 1.0 equiv.), and cesium salt 3a (0.15 mmol, 1.5 equiv.), and the vial was capped. After evacuated and backfilled nitrogen three times, DMSO [0.05 M] and 4,4,5,5-tetramethyl-2-vinyl-1,3,2-dioxaborolane (1, 0.12 mmol, 1.2 equiv.) were added via syringe. The reaction mixture was then irradiated with a 90 W blue LED lamp (at approximately 3 cm away from the light source) with cooling from a fan for 24 h. The reaction was quenched with H₂O, extracted with ethyl acetate. The combined organic layers were dried with Mg₂SO₄, filtered, and concentrated in vacuo. The crude material was purified by flash chromatography (hexane/ethyl acetate = 10:1) to afford the product 4a as a pale yellow oil in 84% yield. ¹H NMR (400 MHz, CDCl₃): δ = 8.48 (d, J = 6.0 Hz, 2 H), 7.13 (d, J = 6.0 Hz, 2 H), 2.57–2.50 (m, 2 H), 1.53–1.48 (m, 2 H), 1.48–1.42 (m, 5 H), 1.34–1.27 (m, 5 H), 0.94 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 153.33, 149.37, 124.07, 43.17, 37.71, 32.87, 29.55, 26.45, 24.86, 22.03. HRMS (ESI+): m/z calcd for C₁₄H₂₂N⁺ [M + H]: 204.1747; found: 204.1741.

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