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

Synlett, Inhaltsverzeichnis

Synlett
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

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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Referenzen

References and Notes

1a Fleming FF, Wang Q. Chem. Rev. 2003; 103: 2035
1b Kurono N, Ohkuma T. ACS Catal. 2016; 6: 989
1c López R, Palomo C. Angew. Chem. Int. Ed. 2015; 54: 13170

2a Zhang L.-H, Wu L, Raymon HK, Chen R, Corral L, Shirley MA, Narla RK, Gamez J, Muller GW, Stirling DI, Bartlett JB, Schafer PH, Payvandi F. Cancer Res. 2006; 66: 951
2b Thanki K, Gangwal RP, Sangamwar AT, Jain S. J. Controlled Release 2013; 170: 15
2c Nitsche C, Steuer C, Klein CD. Bioorg. Med. Chem. 2011; 19: 7318
2d Männistö PT, Kaakkola S. Pharmacol. Toxicol. (Oxford U. K.) 1990; 66: 317
2e Janssen PA. J, Lewi PJ, Arnold E, Daeyaert F, de Jonge M, Heeres J, Koymans L, Vinkers M, Guillemont J, Pasquier E, Kukla M, Ludovici D, Andries K, de Béthune M.-P, Pauwels R, Das K, Clark AD. Jr, Frenkel YV, Hughes SH, Medaer B, De Knaep F, Bohets H, De Clerck F, Lampo A, Williams P, Stoffels P. J. Med. Chem. 2005; 48: 1901
2f Fleming FF, Yao L, Ravikumar PC, Funk L, Shook BC. J. Med. Chem. 2010; 53: 7902

3a Vispute TP, Zhang H, Sanna A, Xiao R, Huber GW. Science 2010; 330: 1222
3b Barta K, Ford PC. Acc. Chem. Res. 2014; 47: 1503

4a Junge K, Papa V, Beller M. Chem. Eur. J. 2019; 25: 122
4b Gunanathan C, Milstein D. Science 2013; 341: 1229712
4c Dobereiner GE, Crabtree RH. Chem. Rev. 2010; 110: 681
4d Crabtree RH. Chem. Rev. 2017; 117: 9228
4e Choi J, MacArthur AH. R, Brookhart M, Goldman AS. Chem. Rev. 2011; 111: 1761

5a Obora Y. ACS Catal. 2014; 4: 3972
5b Hamid MH. S. A, Slatford PA, Williams JM. J. Adv. Synth. Catal. 2007; 349: 1555
5c Chelucci G. Coord. Chem. Rev. 2017; 331: 37

6a Slatford PA, Whittlesey MK, Williams JM. J. Tetrahedron Lett. 2006; 47: 6787
6b Motokura K, Nishimura D, Mori K, Mizugaki T, Ebitani K, Kaneda K. J. Am. Chem. Soc. 2004; 126: 5662
6c Motokura K, Fujita N, Mori K, Mizugaki T, Ebitani K, Htsukawa K, Kanedar K. Chem. Eur. J. 2006; 12: 8228
6d Cheung HW, Li J, Zheng W, Zhou Z, Chiu YH, Lin Z, Lau CP. Dalton Trans. 2010; 39: 265

7 Li F, Zou X, Wang N. Adv. Synth. Catal. 2015; 357: 1405

8a Löfberg C, Grigg R, Whittaker MA, Keep A, Derrick A. J. Org. Chem. 2006; 71: 8023
8b Anxionnat B, Gomez Pardo D, Ricci G, Cossy J. Org. Lett. 2011; 13: 4084

9 Buil ML, Esteruelas MA, Herrero J, Izquierdo S, Pastor IM, Yus M. ACS Catal. 2013; 3: 2072
10 Ma W, Cui S, Sun H, Tang W, Xue D, Li C, Fan J, Xiao J, Wang C. Chem. Eur. J. 2018; 24: 13118
11 Singh A, Findlater M. Organometallics 2021; 41: 3145
12 Bera S, Bera A, Banerjee D. Chem. Commun. 2020; 56: 6850
13 Borghs JC, Tran MA, Sklyaruk J, Rueping M, El-Sepelgy O. J. Org. Chem. 2019; 84: 7927
14 Hall MI, Pridmore SJ, Williams JM. J. Adv. Synth. Catal. 2008; 350: 1975
15 Chakraborty S, Das UK, Ben-David Y, Milstein D. J. Am. Chem. Soc. 2017; 139: 11710
16 Li J, Liu Y, Tang W, Xue D, Li C, Xiao J, Wang C. Chem. Eur. J. 2017; 23: 14445
17 Thiyagarajan S, Gunanathan C. ACS Catal. 2018; 8: 2473

18a Putta RR, Chun S, Lee SB, Hong J, Choi SH, Oh DC, Hong S. J. Org. Chem. 2022; 87: 16378
18b Paudel K, Xu S, Ding K. Org. Lett. 2021; 23: 5028

19a Kolb D, Friedmann K, König B. ChemCatChem 2024; 16: e202400936
19b Bains AK, Yadav A, Adhikari D. Org. Lett. 2021; 23: 2019

20a Zhu M, Tian H, Chen S, Xue W, Wang Y, Lu H, Li T, Chen F, Tang C. J. Catal. 2022; 416: 170
20b Tian H, Xue W, Wu J, Yang Z, Lu H, Tang C. Org. Chem. Front. 2022; 9: 4554
20c Tian H, Lu Y, Tang C. ChemSusChem 2025; 18: e202401244
20d Tian H, Ding C, Liao R, Li M, Tang C. J. Am. Chem. Soc. 2024; 146: 11801

21a Xue W, Zhu Z, Chen S, You B, Tang C. J. Am. Chem. Soc. 2023; 145: 4142
21b Xue W, Jiang Y, Lu H, You B, Wang X, Tang C. Angew. Chem. Int. Ed. 2023; 62: e202314364
21c Sun F, Huang J, Wei Z, Tang C, Liu W. Angew. Chem. Int. Ed. 2023; 62: e202303433
21d Lu Y, Zhu M, Chen S, Yao J, Li T, Wang X, Tang C. J. Am. Chem. Soc. 2024; 146: 23338
21e Jiang Y, Chen S, Chen Y, Gu A, Tang C. J. Am. Chem. Soc. 2024; 146: 2769
21f Chen S, Xue W, Tang C. ChemSusChem 2022; 15: e202201522

22a Srimani D, Leitus G, Ben-David Y, Milstein D. Angew. Chem. Int. Ed. 2014; 53: 11092
22b Beletskaya IP, Najera C, Yus M. Chem. Soc. Rev. 2020; 49: 7101
22c Wang C, Fan Q, Wang G, Zhu Q. Mol. Catal. 2023; 547: 113352

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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