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Synlett 2023; 34(13): 1597-1602
DOI: 10.1055/a-2029-4189
DOI: 10.1055/a-2029-4189
letter
Manganese-Mediated Aerobic Oxidative Denitroalkylation of β-Nitrostyrenes with Alkylboronic Acids
This work was supported by the Natural Science Foundation of Zhejiang Province (No. LY19B020001) and the Special Foundation for Young Scientists of Lishui, Zhejiang (No. 2018RC09).
Abstract
An aerobic oxidative stereoselective denitroalkylation of β-nitrostyrenes under mild conditions by using an alkylboronic acid as the alkyl source was achieved. This protocol accepts a broad scope of β-nitrostyrenes and alkylboronic acids, leading to the formation of C(sp3)–C(sp2) bonds. Air was employed to reoxidize the resultant Mn(II) species back to Mn(III) during the catalytic cycle.
Key words
manganese catalysis - denitroalkylation - alkylboronic acids - nitrostyrenes - radical reaction - aerobic oxidationSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-2029-4189.
- Supporting Information
Publication History
Received: 09 January 2023
Accepted after revision: 06 February 2023
Accepted Manuscript online:
06 February 2023
Article published online:
16 March 2023
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- 11 [(E)-2-Cyclohexylvinyl]benzene (3a); Typical Procedure A 10 mL Schlenk tube equipped with a magnetic stirrer bar was charged with β-nitrostyrene (1a; 0.2 mmol), cyclohexylboronic acid (2a; 0.6 mmol, 3.0 equiv), Mn(OAc)3·2 H2O (0.2 mmol, 1.0 equiv), ligand L6 (0.2 mmol, 1.0 equiv), TFA (0.4 mmol, 2.0 equiv), and DCE (2 mL). The mixture was then stirred at 60 °C under air for 12 h until the reaction was complete (TLC). 10% aq NaHCO3 (20 mL) was added, and the mixture was extracted with CH2Cl2 (3 × 10 mL). The combined extracts were washed with brine, dried (Na2SO4), and concentrated under reduced pressure. The crude residue was purified by column chromatography (silica gel, EtOAc–hexane) to give a colorless oil; yield: 87%. 1H NMR (300 MHz, CDCl3): δ = 7.42–7.30 (m, 4 H), 7.28–7.19 (m, 1 H), 6.40 (d, J = 16.0 Hz, 1 H), 6.23 (dd, J = 16.0, 6.8 Hz, 1 H), 2.21–2.15 (m, 1 H), 1.89–1.71 (m, 5 H), 1.45–1.34 (m, 2 H), 1.29–1.16 (m, 3 H). 13C NMR (75 MHz, CDCl3): δ = 138.11, 136.93, 128.53, 127.26, 126.80, 126.00, 41.25, 33.02, 26.25, 26.13. HRMS (ESI-TOF): m/z [M + H]+ calcd for C14H19: 187.1482; found: 187.1479.