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Synthesis
DOI: 10.1055/a-2641-8389
DOI: 10.1055/a-2641-8389
paper
Green Light-Driven Reduction of Methylenemalononitriles with Formate as a Reductant Without a Thiol Hydrogen-Atom-Transfer Catalyst
This work is supported by the National Natural Science Foundation of China (8217131836).
Abstract
The reduction of methylenemalononitriles to their corresponding methylmalononitriles represents an important transformation in organic synthesis, owing to the ready availability of these starting materials. Herein, we report a safe, cost-effective, and practical photochemical reduction employing readily accessible organophotocatalyst and formate without thiol-mediated HAT catalysts. This method accommodates a broad substrate scope, including diverse (hetero)aryl-substituted methylenemalononitriles, delivering moderate to excellent yields.
Publication History
Received: 24 April 2025
Accepted after revision: 23 June 2025
Accepted Manuscript online:
23 June 2025
Article published online:
31 July 2025
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References
- 1 Li J, Lear MJ, Hayashi Y. Chem Eur J 2021; 27: 5901
- 2 Kelley AM, Frost JA, Baber TM. et al. Tetrahedron Lett 2022; 88: 153573
- 3 Li J, Lear MJ, Hayashi Y. Angew Chem, Int Ed 2016; 55: 9060
- 4 Long J, Lu Z, Li XL, Xue P, Liu WB. Chin J Chem 2024; 42: 873
- 5 Zhang D, Lian M, Liu J. et al. Org Lett 2019; 21: 2597
- 6 Bai Y-Q, Xun S-S, Niu T, Zhou Y-G, Wu B. Org Lett 2025; 27: 1492
- 7 Kang H-Y, Sang Hong W, Seo Cho Y, Yeong Koh H. Tetrahedron Lett 1995; 36: 7661
- 8 Zhang X-W, Li Q-Y, Yan W, Hu X-D, Liu W-B. Org Lett 2025; 27: 1042
- 9a Li R, Zhao B, Chang G. et al. New J Chem 2024; 48: 3573
- 9b Attia YA, Mohamed YMA. New J Chem 2022; 46: 1677
- 9c Qiu C, Sun Y, Xu Y. et al. ChemSusChem 2021; 14: 3344
- 9d Wang H, Wang Y, Jia A. et al. Catal Sci Technol 2017; 7: 5572
- 9e Li X, Zhang B, Fang Y. et al. Chem Eur J 2017; 23: 4266
- 9f Semeniuchenko V, Exner TE, Khilya V, Groth U. Appl Organomet Chem 2011; 25: 804
- 9g Semeniuchenko V, Khilya V, Groth U. Synlett 2009; 271
- 10 Jimenez DEQ, Ferreira IM, Birolli WG, Fonseca LP, Porto ALM. Tetrahedron 2016; 72: 7317
- 11a He Q, Xu Z, Jiang D. et al. RSC Adv 2014; 4: 8671
- 11b Che J, Lam Y. Adv Synth Catal 2010; 352: 1752
- 11c Zhang B, Zhu X-Q, Lu J-Y, He J, Wang PG, Cheng J-P. J Org Chem 2003; 68: 3295
- 11d Garden SJ, Guimaraes CRW, Correa MB, Fernandes de Oliveira CA, Pinto ADC, Bicca de Alencastro R. J Org Chem 2003; 68: 8815
- 12 Feng Y-S, Yang C-Y, Huang Q, Xu H-J. Tetrahedron 2012; 68: 5053
- 13 Bobal P, Bobalova J. Molecules 2013; 18: 2212
- 14 Horn M, Mayr H, Lacote E. et al. Org Lett 2012; 14: 82
- 15a Xue D, Chen Y-C, Cui X, Wang Q-W, Zhu J, Deng J-G. J Org Chem 2005; 70: 3584
- 15b Yang X, Fox T, Berke H. Chem Commun 2011; 47: 2053
- 15c Yang X, Fox T, Berke H. Org Biomol Chem 2012; 10: 852
- 16 Ranu BC, Dutta J, Guchhait SK. Org Lett 2001; 3: 2603
- 17 Noël T, Zysman-Colman E. Chem Catal 2022; 2: 468
- 18 Qiao B, Jiang Z. ChemPhotoChem 2018; 2: 703
- 19 Srivastava V, Singh PK, Singh PPJ. Photochem Photobiol, C 2022; 50: 100488
- 20 Candish L, Collins KD, Cook GC. et al. Chem Rev 2022; 122: 2907
- 21 Lu Z, Shang M, Lu H. Synthesis 2022; 54: 1231
- 22a Li Q-Y, He Y, Lin Y-M, Gong L. Chem Eur J 2023; 29: e202302542
- 22b Li J, Zhao J, Loh T-P. Synlett 2024; 35: 840
- 23 Das A, Gouthaman S, Justin Thomas KR. Green Chem 2024; 26: 1223
- 24 Zhang L, Sheng G, Yang W. et al. ACS Catal 2024; 14: 11808
- 25 Zheng C, You S-L. Chem Soc Rev 2012; 41: 2498
- 26 Yang Y-Q, Lu Z. Chin J Chem 2014; 32: 650
- 27 Gilkey MJ, Xu B. ACS Catal 2016; 6: 1420
- 28 Pavlova A, Rösler E, Meijer EJ. ACS Catal 2016; 6: 5350
- 29a Narayanam JMR, Tucker JW, Stephenson CRJ. J Am Chem Soc 2009; 131: 8756
- 29b Nguyen JD, D'Amato EM, Narayanam JMR, Stephenson CRJ. Nat Chem 2012; 4: 854
- 30a Nguyen JD, Matsuura BS, Stephenson CR. J Am Chem Soc 2014; 136: 1218
- 30b Speckmeier E, Fischer TG, Zeitler K. J Am Chem Soc 2018; 140: 15353
- 31 Brzezinski CU, LeBlanc AR, Clerici MG, Wuest WM. Org Lett 2024; 26: 5534
- 32 Hart H, Kim YC. J Org Chem 2002; 31: 2784
- 33 DMSO is suggsted by a reviewer from European Journal of Organic Chemistry
- 34 Hendy CM, Smith GC, Xu Z, Lian T, Jui NT. J Am Chem Soc 2021; 143: 8987
- 35 Chmiel AF, Williams OP, Chernowsky CP, Yeung CS, Wickens ZK. J Am Chem Soc 2021; 143: 10882
- 36 Romero NA, Nicewicz DA. Chem Rev 2016; 116: 10075
- 37 Koppenol WH, Rush JD. J Phys Chem 1987; 91: 4429
- 38 Potential originally reported relative to NHE reference electrode; referenced to SCE by subtracting 0.241 V from the reported value
- 39 Tayyari F, Wood DE, Fanwick PE, Sammelson RE. Synthesis 2008; 2008: 279
- 40 He Q, Xu Z, Jiang D. et al. RSC Adv 2014; 4: 8671
- 41 Jedinak L, Krystof V, Cankar P. Heterocycles 2011; 83: 371
- 42 He T, Shi R, Gong Y. et al. Synlett 2016; 27: 1864
- 43 Campaigne E, Roelofs WL. J Org Chem 1965; 30: 396