Synthesis of Alkenyl Nitriles by Bidentate Cobalt-Catalyzed Acceptorless Dehydrogenation Coupling of Alcohols and Nitriles

Zhaolun Zhang; Sanxia Chen; Haitao Tian; Conghui Tang

doi:10.1055/a-2552-5614

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DOI: 10.1055/a-2552-5614

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First-Row Transition-Metal Catalysis for Organic Synthesis

Synthesis of Alkenyl Nitriles by Bidentate Cobalt-Catalyzed Acceptorless Dehydrogenation Coupling of Alcohols and Nitriles

Zhaolun Zhang‡

^aKey Laboratory of Material Chemistry for Energy Conversion and Storage (Ministry of Education), Hubei Key Laboratory of Material Chemistry and Service Failure, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan, P. R. of China

,

Sanxia Chen‡

^aKey Laboratory of Material Chemistry for Energy Conversion and Storage (Ministry of Education), Hubei Key Laboratory of Material Chemistry and Service Failure, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan, P. R. of China

,

Haitao Tian∗

^aKey Laboratory of Material Chemistry for Energy Conversion and Storage (Ministry of Education), Hubei Key Laboratory of Material Chemistry and Service Failure, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan, P. R. of China

,

Conghui Tang ∗

^aKey Laboratory of Material Chemistry for Energy Conversion and Storage (Ministry of Education), Hubei Key Laboratory of Material Chemistry and Service Failure, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan, P. R. of China

^bState Key Laboratory of Natural and Biomimetic Drugs, Peking University, Beijing, P. R. of China

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Abstract

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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.

Key word

cobalt catalysis - dehydrogenation - alkenyl nitriles - oleﬁnation - nitriles - alcohols

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References and Notes

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23 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; R_f = 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.

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