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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  ∗
We thank the National Natural Science Foundation of China (Grant Numbers 21971036 and 21901036), the Shanghai Rising-Star Program (Grant Number 20QA1400200), and the Fundamental Research Funds for the Central Universities for financial support.
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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

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-1320-6946.
  • Supporting Information


Publication History

Received: 29 October 2020

Accepted after revision: 23 November 2020

Accepted Manuscript online:
23 November 2020

Article published online:
16 December 2020

© 2020. Thieme. All rights reserved

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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.