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Synlett
DOI: 10.1055/a-2552-5614
DOI: 10.1055/a-2552-5614
letter
First-Row Transition-Metal Catalysis for Organic Synthesis
Synthesis of Alkenyl Nitriles by Bidentate Cobalt-Catalyzed Acceptorless Dehydrogenation Coupling of Alcohols and Nitriles
This work was supported by the National Natural Science Foundation of China (22371083, 22001086), the Fundamental Research Funds for the Central Universities (2024BRB003, HUST 2020kfyXJJS094), the State Key Laboratory of Natural and Biomimetic Drugs, Peking University (K202409), and the Innovation and Talent Recruitment Base of New Energy Chemistry and Device (B21003).
Abstract
A bidentate Co(III)-catalyzed α-olefination of nitriles has been developed. This one-pot protocol provides a simple procedure for the synthesis of alkenyl nitriles from diverse alcohols and nitriles. An extensive substrate scope, good functional-group compatibility, and high atom economy are displayed. Preliminary mechanistic studies revealed that C=C bond formation proceeds through activation of the O–H bond of the alcohol via an unsaturated 16-electron intermediate cobalt complex, and subsequent condensation of the in situ-formed aldehyde with the nitrile. Remarkably, this method liberates H2 and H2O as the only byproducts.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-2552-5614.
- Supporting Information
Publication History
Received: 02 January 2025
Accepted after revision: 06 March 2025
Accepted Manuscript online:
06 March 2025
Article published online:
14 April 2025
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Alkenyl Nitriles 3; General Procedure
A 25 mL Schlenk tube containing a stirring bar was charged with the appropriate nitrile 1 (0.2 mmol, 1 equiv), [Cp*Co(t-BuPPH)I]+I– (10.0 mol%), and NaOH (1.0 equiv), and the system was evacuated and refilled with argon three times. The alcohol 2 (0.2 mmol, 1.0 equiv) and anhyd toluene (1.0 mL) were added successively, and the mixture was stirred at 100 °C for 24 h. The mixture was then cooled to r.t., diluted with EtOAc, and passed through Celite. The solvent was removed in vacuo and the crude product was purified by TLC.
(2Z)-2-(4-Methoxyphenyl)-3-phenylacrylonitrile (3a)
Prepared by the general procedure and isolated by TLC [silica gel, PE–EtOAc (10:1)] as yellow crystals; yield: 43.3 mg (92%); mp 56–61 °C; Rf
= 0.49 (PE–EtOAc, 10:1, UV).
IR (KBr): 2918 (m), 2214 (m), 1606 (s), 1511 (s), 1256 (s), 1180 (s), 1031 (m), 835 (m), 771 (m), 694 (m), 627 (w), 577 (w), 530 (m), 432 (w) cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.86 (d, J = 7.5 Hz, 2 H), 7.67–7.58 (m, 2 H), 7.50–7.38 (m, 4 H), 7.01–6.92 (m, 2 H), 3.86 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 160.6, 140.3, 134.1, 130.3, 129.2, 129.0, 127.5, 127.1, 118.3, 114.6, 111.4, 55.6. LRMS ESI: m/z [M + H]+ calcd for C16H14NO: 236.1; found: 236.1.