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DOI: 10.1055/a-2774-2259
Benzylic C(sp3)–H Functionalization by Photo Redox Catalysis
Authors
G. P. thanks SERB, New Delhi, for the award of the National Science Chair (NSC/2021/000024). K. S. S. thanks the University Grants Commission (UGC-JRF), New Delhi, for the research fellowship. S.K.R, thanks for (UGC-NFSC), the authors are also grateful to the BHU and SATHI-BHU for their analytical support.

Abstract
Benzylic C–H bonds, due to their enhanced reactivity, offer a valuable platform for the selective functionalization in organic synthesis. Recent advancements in catalytic methods have enabled direct transformation of these sp3-hybridized sites under mild conditions. Transition-metal catalysis, photo redox strategies, and radical pathways have shown particular promise. These approaches allow for the construction of diverse C–C and C–X (X = N, O, Br, S) bonds. The presence of electron-withdrawing groups on the substrates significantly reduces the reaction efficiency, representing a limitation of these methodologies. The ability to functionalize benzylic positions through intermolecular and intramolecular methods expand the toolbox for late-stage modification of complex molecules. Such transformations are increasingly important in pharmaceutical and materials chemistry.
Publication History
Received: 24 September 2025
Accepted after revision: 10 December 2025
Article published online:
15 January 2026
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References
- 1a Blakemore DC, Castro L, Churcher I. et al. Nat Chem 2018; 10: 383-394
- 1b Govaerts S, Nyuchev A, Noël T. J Flow Chem 2020; 10: 13-71
- 1c Xue X, Ji P, Zhou B, Cheng J. Chem Rev 2017; 117: 8622-8648
- 1d Oliva M, Coppola GA, Van der Eycken EV, Sharma UK. Adv Synth Catal 2021; 363: 1810-1834
- 2a Xuan J, Zhang Z-G, Xiao W-J. Angew Chem Int Ed 2015; 54: 15632-15641
- 2b Sharma A, Hartwig JF. Nature 2015; 517: 600-604
- 3a Yan M, Kawamata Y, Baran PS. Chem Rev 2017; 117: 13230-13319
- 3b Frontana-Uribe BA, Little RD, Ibanez JG, Palma A, Vasquez-Medrano R. Green Chem 2010; 12: 2099-2119
- 4a Pandey G, Koley S, Talukdar R, Sahani PK. Org Lett 2018; 20 (18) 5861-5865
- 4b Pandey G, Tiwari SK, Singh B, Vanka K, Jain S. Chem Commun 2017; 53: 12337-12340
- 4c Pandey G, Jadhav D, Tiwari SK, Singh B. Adv Synth Catal 2014; 356: 2813-2818
- 4d Pandey G, Tiwari SK, Singh B. Tetrahedron Lett 2016; 57: 4480-4483
- 4e Pandey G, Singh D, Laha R. Asian J Org Chem 2017; 6: 469-474
- 4f Pandey G, Tiwari SK, Singh P, Mondal PK. Org Lett 2021; 23 (20) 7730-7734
- 4g Mondal PK, Tiwari SK, Singh P, Pandey GJ. Org Chem 2021; 86 (23) 17184-17196
- 4h Ghosh MK, Sharma KS, Pandey G. Org Biomol Chem 2023; 21: 538-550
- 6a Anderson CP, Salmon DJ, Meyer TJ, Young RC. J Am Chem Soc 1977; 99: 1980
- 6b Kohls P, Jadhav D, Pandey G, Reiser O. Org Lett 2012; 14 (22) 672-675
- 7a Condie AG, Gonzalez-Gomez JC, Stephenson CRJ. J Am Chem Soc 2010; 132: 1464
- 7b Hari DP, König B. Org Lett 2011; 13: 3852
- 7c Rueping M, Vila C, Koenigs RM, Poscharny K, Fabry DC. Chem Commun 2011; 47: 2360
- 7d Rueping M, Zhu S, Koenigs RM. Chem Commun 2011; 47: 8679-8681
- 8 Liu Q, Li Y-N, Zhang H-H, Chen B, Tung C-H, Wu L-Z. Chem Eur J 2012; 18: 620-627
- 9 McNally A, Prier CK, MacMillan DWC. Science 2011; 334 (6059) 1114-1117
- 10 Freeman DB, Furst L, Condie AG, Stephenson CRJ. Org Lett 2012; 14 (01) 94-97
- 11a Pandey G, Pal S, Laha R. Angew Chem Int Ed 2013; 52: 5146-5149
- 11b Xuan J, Cheng Y, An J, Lu L-Q, Zhang X-X, Xiao W-J. Angew Chem 2013; 125: 5250-5253
- 12a Photoinduced SET initiated reactions: Generation and synthetic application of arene radical cations”: A. Krishna, Ph.D. Thesis entitled, submitted to Osmania University, Hyderabad, India, 1989
- 12b Pac C, Nakasone A, Sakurai H. J Am Chem Soc 1977; 99: 5806-5808
- 13a Sheldon RA, Kochi JK. Metal Catalyzed Oxidations of Organic Compounds. New York: Academic Press; 1981
- 13b Cainelli G, Cardillo G. Chromium Oxidations in Organic Chemistry. Berlin: Springer; 1984
- 13c Hudlicky M. Oxidion in Organic Chemistry. Washington, DC: American Chemical Society; 1990
- 13d Recupero M, Punta C. Chem Rev 2007; 107: 3800-3842
- 14 Pandey G, Laha R. Angew Chem Int Ed 2015; 54: 14875-14879
- 15 Pandey G, Laha R, Singh D. J Org Chem 2016; 81 (16) 7161-7171
- 16a Lowry MS, Goldsmith JI, Slinker JD. et al. Chem Mater 2005; 17: 5712
- 16b Tucker JW, Narayanam JMR, Shah PS, Stephenson CRJ. Chem Commun 2011; 47: 5040
- 17 Pandey G, Laha R, Mondal PK. Chem Commun 2019; 55: 9689-9692
- 18a Lingamurthy M, Jagadeesh Y, Ramakrishna K, Rao BV. J Org Chem 2016; 81: 1367
- 18b Yamaguchi M, Itagaki D, Ueda H, Tokuyama H. J Antibiot (Tokyo) 2016; 69: 253
- 19a Rogano F, Rüedl P. Chim Acta 2010; 93: 1281-1298
- 19b Vyvyan JR, Longworth HE, Nguyen SK. Synlett 2016; 27: 2221
- 20 Swati Sharma K, Kumar Tiwari S, Pandey G. Asian J Org Chem 2024; 13 (08) No. e202400114
- 21a Zhang YJ, Abe T, Tanaka T, Yang CR, Kouno I. J Nat Prod 2001; 64: 1527-1532
- 21b Beck JJ, Chou SC. J Nat Prod 2007; 70: 891-900
- 22a Collins IJ. J Chem Soc Perkin Trans 1998; 1: 1869-1888
- 22b Hirata A, Kim SY, Kobayakawa N, Tanaka N, Kashiwada Y. Fitoterapia 2015; 102: 49-55
- 22c Devon TK, Scott AI. Handbook of Naturally Occurring Compounds. Vol. 1. New York: Academic Press; 1975: 249
- 23a Maso MJD, Nepomuceno GM, St Peter MA, Gitre HH, Martin KS, Shaw JT. Org Lett 2016; 18: 1740-1743
- 23b Fu TH, McElroy WT, Shamszad M, Martin SF. Org Lett 2012; 14: 3834-3837
- 23c Shenvi RA, Corey EJ. J Am Chem Soc 2009; 131: 5746-5747
- 23d Masse CE, Morgan AJ, Adams J, Panek JS. Eur J Org Chem 2000; 2513-2528
- 24a Shen DY, Nguyen TN, Wu SJ. et al. J Nat Prod 2015; 78: 2521-2530
- 24b Okazaki Y, Ishizuka A, Ishihara A, Nishioka T, Iwamura HJ. Org Chem 2007; 72: 3830-3839
- 24c Caruano J, Muccioli GG, Robiette R. Org Biomol Chem 2016; 14: 10134-10156
- 25 Sharma KS, Thadem N, Pandey G. J Org Chem 2025; 90: 3384-3390
- 26 Zhang Z, Butt NA, Zhang W. Chem Rev 2016; 116 (22) 14769-14827
- 27 Jiang W, Li N, Zhou L, Zeng Q. ACS Catal 2018; 8 (11) 9899-9906
- 28 Xiong B, Xu S, Liu Y, Tang K-W, Wong W-Y. J Org Chem 2021; 86 (03) 1516-1527