Dual Nickel/Photoredox-Catalyzed Stereoselective Allylation for the Synthesis of 1,3-Diols

Xinyi Zhang; Heyang Xu; Zhixian Wu; Xiaobo Ding; Qingyu Shi; Yizhe Mao; Lei Shi

doi:10.1055/a-2640-2384

Synlett, Table of Contents

Synlett
DOI: 10.1055/a-2640-2384

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Dual Nickel/Photoredox-Catalyzed Stereoselective Allylation for the Synthesis of 1,3-Diols

Xinyi Zhang

¹School of Chemistry, Dalian University of Technology, Dalian, Liaoning 116024, PR China

,

Heyang Xu

¹School of Chemistry, Dalian University of Technology, Dalian, Liaoning 116024, PR China

,

Zhixian Wu

¹School of Chemistry, Dalian University of Technology, Dalian, Liaoning 116024, PR China

,

Xiaobo Ding

¹School of Chemistry, Dalian University of Technology, Dalian, Liaoning 116024, PR China

,

Qingyu Shi

¹School of Chemistry, Dalian University of Technology, Dalian, Liaoning 116024, PR China

,

Yizhe Mao

¹School of Chemistry, Dalian University of Technology, Dalian, Liaoning 116024, PR China

,

Lei Shi

¹School of Chemistry, Dalian University of Technology, Dalian, Liaoning 116024, PR China

²School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan 453007, PR China

› Author Affiliations

Abstract

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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 carbon

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References

References

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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, R_f = 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

Supplementary Material

Supplementary Material