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Synlett
DOI: 10.1055/a-2640-2384
DOI: 10.1055/a-2640-2384
letter
Dual Nickel/Photoredox-Catalyzed Stereoselective Allylation for the Synthesis of 1,3-Diols
Supported by: Foundation of China 22171036,22471029
Supported by: School of Chemistry and Chemical Engineering, Henan Normal University 2020YB03
Supported by: Natural Science Foundation of Henan Province 232300421126
Funding Information Foundation of China (22471029 and 22171036), the Natural Science Foundation of Henan Province (232300421126), and the Open Research Fund of the School of Chemistry and Chemical Engineering, Henan Normal University (2020YB03).
Abstract
An efficient dual Ni/organophotoredox catalytic system has been developed for the stereoselective allylation of aldehydes with vinyl cyclic carbonates (VCCs). This method enables the construction of 1,3-diols bearing tertiary stereocenters under mild conditions (room temperature, visible light irradiation) with excellent yields (up to 89%) and diastereoselectivity (dr >20:1). Key to the success is the synergistic interplay between nickel catalysis and photoredox activation, which facilitates the generation of nucleophilic allyl-Ni intermediates and subsequent C–C bond formation via a Zimmerman–Traxler-type transition state. The protocol employs inexpensive and commercially available catalysts, exhibits broad substrate scope, and demonstrates applicability to late-stage functionalization of pharmaceuticals.
Keywords
Photocatalysis - Nickel catalysis - Allylation - Stereoselectivity - 1,3-Diols - Quaternary carbonPublication History
Received: 02 April 2025
Accepted after revision: 19 June 2025
Accepted Manuscript online:
20 June 2025
Article published online:
30 July 2025
© 2025. Thieme. All rights reserved.
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- 19 3a General Procedure. In a clean, oven-dried screw-cap reaction tube containing a magnetic stir bar, aldehyde (0.1 mmol), VCCs (0.2 mmol, 2 eq.), DIPEA (1 eq.), HE (3 mmol, 1.5 eq.), 4CzIPN (2.0 mol%) were weighed. NiCl2 (10 mol%,), ligand (12 mol%,) with THF (1 mL, 0.1M) were stirring together in N2 atmosphere overnight. A common laboratory syringe was used to introduce mixed liquor (1 mL) into the reaction mixture. Then, the reaction mixture was stirred at room temperature using a 10 W 455 nm LED for 4 h. After detaching the reaction, the solvent was removed in a rotatory evaporator. Finally, it was concentrated in reduced pressure and was purified by column chromatography through silica gel (300−400 mesh size) using PET-ether/ethyl acetate as an eluent an eluent silica gel (300−400 mesh size) using PET-ether/ethyl acetate as an eluent
- 20 3a, Rf = 0.3 (EA/PE = 1:5), the eluent: EA/PE = 1:10, 85% (136.1 mg), white solid. 1H NMR (400 MHz, Chloroform-d) δ 7.86–7.77 (m, 1H), 7.77–7.70 (m, 1H), 7.63 (d, J = 8.4Hz, 1H), 7.56 (s, 1H), 7.48 (qd, J = 6.8, 3.4 Hz, 2H), 7.34 –7.15 (m, 5H), 7.09 (dd, J = 8.4, 2.0 Hz, 1H), 6.30 (dd, J = 18.0, 11.2 Hz, 1H), 5.45 (d, J = 11.2 Hz, 1H), 5.39 (s, 1H), 5.18 (d, J = 18.0 Hz, 1H), 4.03 (d, J = 11.2 Hz, 1H), 3.79 (d, J = 10.8 Hz, 1H), 3.39 (s, 1H), 2.38 (s, 1H). 13C NMR (101 MHz, Chloroform-d) δ 140.51, 139.18, 137.78, 132.77, 132.56, 128.34, 128.15, 128.01, 127.43, 126.90, 126.76, 126.64, 125.93, 125.79, 125.77, 117.51, 77.93, 65.75, 54.72. HRMS-ESI (m/z) [M+Cl]− Chemical Formula: C21H20ClO2 Exact Mass: 339.1152; found: 339.1160