Recent Advances in Photocatalytic Reactions with Isocyanides

doi:10.6023/cjoc202206012

Abstract

Isocyanides are a class of valuable C1 building blocks, widely used in organic chemistry, combinatorial chemistry, biomedicine and other fields, and their derivatives are effective building blocks for the synthesis of bioactive molecules and complex natural products. Herein, the recent advances in photocatalytic reactions with isocyanides are summarized according to the types of the reaction mechanism. The photocatalyst, substrate range and reaction mechanism are emphatically discussed. Finally, the challenges and future development trends of this research field are discussed and prospected.

Key words: isocyanide, visible light photocatalysis, cooperative photocatalysis, transition metal-based photocatalyst

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Yan He, Tianzi Huang, Xiaoqin Shi, Yan Chen, Qiong Wu. Recent Advances in Photocatalytic Reactions with Isocyanides[J]. Chinese Journal of Organic Chemistry, 2022, 42(12): 4220-4246.

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Fig. & Tab. 33

Figure 1. Development history of visible light catalysis in organic synthesis

Figure 2. Visible light-induced transformations via (a) conventional photocatalysis, (b) cooperative photocatalysis, and (c) visible light-induced transition metal catalysis

Figure 3. Mechanisms of photocatalysis

Scheme 1. Visible-light-induced SET pathways

Entry	Photocatalyst	E_1/2(M⁺/M*)/V	E_1/2(M*/M^–)/V	E_1/2(M⁺/M)/V	E_1/2(M/M^–)/V	Ref.
1	fac-Ir(ppy)₃	–1.73	+0.31	+0.77	–2.19	[13]
2	Ir[dF(CF₃)ppy]₂(dtb-bpy)⁺	–0.89	+1.21	+1.69	–1.37	[14]
3	[Ir(ppy)₂(dtbbpy)]⁺	–0.96	+0.66	+1.21	–1.51	[14,15]
4	Ru(bpy)₃²⁺	–0.81	+0.77	+1.29	–1.33	[16]
5	Cz-NI	–1.67	+1.28	+1.01	–1.40	[17]
6	MANI	–1.67	+1.11	+0.99	–1.55	[17]
7	Rose Bengal	–0.68	+0.99	+1.09	–0.78	[18]
8	Eosin Y	–1.60	+1.18	+0.72	–1.14	[18]

Table 1. Redox potentials of commonly utilized visible light photocatalysts

Figure 4. Representative catalysts for photochemical reactions through SET pathways

Scheme 2. Ir-catalyzed photoredox-mediated radical process to synthesize 2-aryl or 2-phenylthio-indoleethyl 3-glyoxylates

Scheme 3. A visible-light-induced radical cascade cyclization of aryl isonitriles and cyclobutanone oxime esters for the synthesis of cyclopenta-[b]quinoxalines

Scheme 4. A visible-light-induced radical cascade cyclization of 2-isocyanoaryl thioethers

Scheme 5. Iridium-catalyzed visible lightinduced decarboxylative cyclization of 2-alkenylarylisocyanides with α-oxocarboxylic acids

Scheme 6. Iridium-catalyzed visible-light-driven radical difluoromethylation of isocyanides to access difluoromethylated phenanthridines and isoquinolines

Scheme 7. Visible-light photocatalytic functionalization of isocyanides for the synthesis of secondary amides and ketene aminals

Scheme 8. Photocatalytic isocyanide-based multicomponent domino cascade reaction

Scheme 9. Visible-light-induced radical isocyanide insertion reactions between 3-(2-isocyanobenzyl)-indoles and bromodifluoroacetates or bromodifluoroacetamides

Scheme 10. Synthesis of 6-alkylated phenanthridines using xanthates as radical precursors under visiblelight photoredox catalysis

Scheme 11. A visible-light-induced radical cascade cyclization of ortho-diisocyanoarenes for the synthesis of diethyl benzo[a]phenazine-6,6(5H)-dicarboxylates

Scheme 12. Visible-light-induced, Rh-catalyzed cyclization of arylthiodifluoromethyl 2-pyridyl sulfone with isocyanides for the synthesis of phenanthridines

Scheme 13. Visible-light-mediated protocol for the synthesis of ring cores of camptothecins

Scheme 14. Visible-light-mediated protocol for the synthesis of 6-alkylated phenanthridine derivatives

Scheme 15. Visible-light-induced, manganese-catalyzed tandem cyclization of 2-biphenyl isocyanides with cyclopropanols for the synthesis of 6-β-ketoalkyl phenanthridines

Scheme 16. Visible-light-enabled construction of thiocarbamates from isocyanides, thiols and water

Scheme 17. Synthesis of 6-thiocyanatophenanthridines by visible-light- and air-promoted radical thiocyanation of 2-isocyanobiphenyls

Scheme 18. Visible-light-mediated metal-free decarboxylative acylations of isocyanides with α-oxocarboxylic acids and water leading to α-ketoamides

Scheme 19. Visible-light-mediated Rose Bengal-catalyzed phosphorylation of 2-isocyanoaryl thioethers

Scheme 20. Eosin Y-catalyzed multicomponent reaction of styrene, 2-aminopyrimidine and tert-butyl isocyanide

Scheme 21. Eosin Y-catalyzed cyclization of o-alkenylanilines and isocyanides

Scheme 22. fac-Ir(ppy)3-catalyzed isonitrile-involved SET and EnT synergistic mechanism

Scheme 23. Synthesis of 3-aminoimidazo[1,2-a]pyridines via the HAT mechanism

Scheme 24. Photoredox catalysis toward 2?sulfenylindole synthesis through a radical cascade process

Scheme 25. Photoinduced metal-free α-C(sp3)—H carbamoylation of saturated aza-heterocycles via Cz-NI organic photocatalyst

Scheme 26. 4CzIPN-tBu-catalyzed proton-coupled electron transfer for photosynthesis of phosphorylated N?heteroaromatics

Scheme 27. Visible light-promoted dual nickel- and photoredox catalyzed spirocyclization of isocyanides with 1,5-enynes

Scheme 28. Visible-light-induced Pd-catalyzed three-component 1,2-alkyl functionalization of alkenes with alkyl iodides and isocyanides

References 52

[1]	Schultz, D. M.; Yoon, T. P. Science 2014, 343, 985.
[2]	Ciamician, G. Science 1912, 36, 385. pmid: 17836492
[3]	Cano-Yelo, H.; Deronzier, A. J. Chem. Soc., 1984, 1093.
[4]	König, B. Eur. J. Org. Chem. 2017, 1979.
[5]	Pandey, G.; Hajra, S.; Ghorai, M. K.; Kumar, K. R. J. Am. Chem. Soc. 1997, 119, 8777. doi: 10.1021/ja9641564
[6]	Nicewicz, D. A.; MacMillan, D. W. C. Science 2008, 322, 77. doi: 10.1126/science.1161976 pmid: 18772399
[7]	(a) Tucker, J. W.; Stephenson, C. R. J. J. Org. Chem. 2012, 77, 1617. doi: 10.1021/jo202538x
	(b) Prier, C. K.; Rankic, D. A.; MacMillan, D. W. C. Chem. Rev. 2013, 113, 5322. doi: 10.1021/cr300503r
	(c) Schultz, D. M.; Yoon, T. P. Science 2014, 343, 1239176. doi: 10.1126/science.1239176
	(d) Meggers, E. Chem. Commun. 2015, 51, 3290. doi: 10.1039/C4CC09268F
	(e) Romero, N. A.; Nicewicz, D. A. Chem. Rev. 2016, 116, 10075. doi: 10.1021/acs.chemrev.6b00057
[8]	(a) Tellis, J. C.; Kelly, C. B.; Primer, D. N.; Jouffroy, M.; Patel, N. R.; Molander, G. A. Acc. Chem. Res. 2016, 49, 1429. doi: 10.1021/acs.accounts.6b00214
	(b) Skubi, K. L.; Blum, T. R.; Yoon, T. P. Chem. Rev. 2016, 116, 10035. doi: 10.1021/acs.chemrev.6b00018
	(c) Lang, X.; Zhao, J.; Chen, X. Chem. Soc. Rev. 2016, 45, 3026. doi: 10.1039/C5CS00659G
[9]	(a) Nenaydenko, V. G. Isocyanide Chemistry: Applications in Synthesis and Material Science, Wiley-VCH, Weinheim, Germany, 2012. pmid: 29620903
	(b) Qiu, G.; Ding, Q.; Wu, J. Chem. Soc. Rev. 2013, 42, 5257. doi: 10.1039/c3cs35507a pmid: 29620903
	(c) Liu, J.; Fang, Z.; Zhang, Q.; Liu, Q.; Bi, X. Angew. Chem., Int. Ed. 2013, 52, 6953. doi: 10.1002/anie.201302024 pmid: 29620903
	(d) Rotstein, B. H.; Zaretsky, S.; Rai, V.; Yudin, A. K. Chem. Rev. 2014, 114, 8323. doi: 10.1021/cr400615v pmid: 29620903
	(e) He, Y.; Wang, Y.-C.; Hu, K.; Xu, X.-L.; Wang, H.-S.; Pan, Y.-M. J. Org. Chem. 2016, 81, 11813. doi: 10.1021/acs.joc.6b02288 pmid: 29620903
	(f) Song, B.; Xu, B. Chem. Soc. Rev. 2017, 46, 1103. doi: 10.1039/C6CS00384B pmid: 29620903
	(g) Giustiniano, M.; Basso, A.; Mercalli, V.; Massarotti, A.; Novellino, E.; Tron, G. C.; Zhu, J. Chem. Soc. Rev. 2017, 46, 1295. doi: 10.1039/C6CS00444J pmid: 29620903
	(h) Zhang, R.; Gu, Z.-Y.; Wang, S.-Y.; Ji, S.-J. Org. Lett. 2018, 20, 5510. doi: 10.1021/acs.orglett.8b02516 pmid: 29620903
	(i) Wan, J.-P.; Gana, L.; Liu, Y. Org. Biomol. Chem. 2017, 15, 9031. doi: 10.1039/C7OB02011B pmid: 29620903
	(j) He, Y.; Wang, Y.; Liang, X.; Huang, B.; Wang, H.; Pan, Y.-M. Org. Lett. 2018, 20, 7117. doi: 10.1021/acs.orglett.8b03068 pmid: 29620903
	(k) Tong, W.; Li, W.-H.; He, Y.; Mo, Z.-Y.; Tang, H.-T.; Wang, H.-S.; Pan, Y.-M. Org. Lett. 2018, 20, 2494. doi: 10.1021/acs.orglett.8b00886 pmid: 29620903
	(l) Cao, M.; Liu, L. Tang, S.; Peng, Z.; Wang, Y. Adv. Synth. Catal. 2019, 361, 1887. doi: 10.1002/adsc.201801245 pmid: 29620903
	(m) Wang, M.-R.; Deng, L.; Liu, G.-C.; Wen, L.; Wang, J.-G.; Huang, K.-B.; Tang, H.-T.; Pan, Y.-M. Org. Lett. 2019, 21, 4929. doi: 10.1021/acs.orglett.9b01230 pmid: 29620903
	(n) Cao, M.; Fang, Y.-L.; Wang, Y.-C.; Xu, X.-J.; Xi, Z.-W.; Tang, S. ACS Comb. Sci. 2020, 22, 268. doi: 10.1021/acscombsci.0c00012 pmid: 29620903
	(o) Cao, M.; Teng, Q.-H.; Xi, Z.-W.; Liu, L.-Q.; Gu, R.-Y.; Wang, Y.-C. Org. Biomol. Chem. 2020, 18, 655. doi: 10.1039/C9OB02337B pmid: 29620903
	(p) Xi, Z.-W.; He, Y.; Liu, L.-Q.; Wang, Y.-C. Org. Biomol. Chem. 2020, 18, 8089. doi: 10.1039/D0OB01604G pmid: 29620903
	(q) Li, Y.; Miao, T.; Li, P.; Wang, L. Org. Lett. 2018, 20, 1735. doi: 10.1021/acs.orglett.8b00171 pmid: 29620903
[10]	Ren, X.; Lu, Z. Chin. J. Catal. 2019, 40, 1003.
[11]	Heitz, D. R.; Tellis, J. C.; Molander, G. A. J. Am. Chem. Soc. 2016, 138, 12715. pmid: 27653500
[12]	Hoffmann, N. Eur. J. Org. Chem. 2017, 15, 1982.
[13]	Flamigni, L.; Barbieri, A.; Sabatini, C.; Ventura, B.; Barigelletti, F. Top. Curr. Chem. 2007, 281, 143.
[14]	Lowry, M. S.; Goldsmith, J. I.; Slinker, J. D.; Rohl, R.; Pascal, R. A.; Malliaras, G. G.; Bernhard, S. Chem. Mater. 2005, 17, 5712. doi: 10.1021/cm051312+
[15]	Slinker, J. D.; Gorodetsky, A. A.; Lowry, M. S.; Wang, J.; Parker, S.; Rohl, R.; Bernhard, S.; Malliaras, G. G. J. Am. Chem. Soc. 2004, 126, 2763. pmid: 14995193
[16]	(a) Kalyanasundaram, K. Coord. Chem. Rev. 1982, 46, 159. doi: 10.1016/0010-8545(82)85003-0
	(b) Juris, A.; Balzani, V.; Belser, P.; von Zelewsky, A. Helv. Chim. Acta 1981, 64, 2175. doi: 10.1002/hlca.19810640723
[17]	Yi, M.-J.; Zhang, H.-X.; Xiao, T.-F.; Zhang, J.-H.; Feng, Z.-T.; Wei, L.-P.; Xu, G.-Q.; Xu, P.-F. ACS Catal. 2021, 11, 3466. doi: 10.1021/acscatal.1c00242
[18]	Ravelli, D.; Fagnonia, M.; Albini, A. Chem. Soc. Rev. 2013, 42, 97. doi: 10.1039/c2cs35250h pmid: 22990664
[19]	Vidyasagar, A.; Shi, J.; Kreitmeier, P.; Reiser, O. Org. Lett. 2018, 20, 6984. doi: 10.1021/acs.orglett.8b02725 pmid: 30398887
[20]	Yuan, Y.; Dong, W.-H.; Gao, X.-S.; Xie, X.-M.; Zhang, Z.-G.; Chem. Commun. 2019, 55, 11900. doi: 10.1039/C9CC05655F
[21]	Yuan, Y.; Dong, W.; Gao, X.; Xie, X.; Zhang, Z. Org. Lett. 2019, 21, 469. doi: 10.1021/acs.orglett.8b03710 pmid: 30588818
[22]	Zhang, X.; Zhu, P.; Zhang, R.; Li, X.; Yao, T. J. Org. Chem. 2020, 85, 9503. doi: 10.1021/acs.joc.0c00039
[23]	Qin, W.-B.; Xiong, W.; Li, X.; Chen, J.-Y.; Lin, L.-T.; Wong, H. N. C.; Liu, G.-K. J. Org. Chem. 2020, 85, 10479. doi: 10.1021/acs.joc.0c00816
[24]	Cannalire, R.; Amato, J.; Summa, V.; Novellino, E.; Tron, G. C.; Giustiniano, M. J. Org. Chem. 2020, 85, 14077. doi: 10.1021/acs.joc.0c01946 pmid: 33074674
[25]	Pelliccia, S.; Alfano, A. I.; Luciano, P.; Novellino, E.; Massarotti, A.; Tron, G. C.; Ravelli, D.; Giustiniano, M. J. Org. Chem. 2020, 85, 1981. doi: 10.1021/acs.joc.9b02709 pmid: 31880934
[26]	Cannalire, R.; Santoro, F.; Russo, C.; Graziani, G.; Tron, G. C.; Carotenuto, A.; Brancaccio, D.; Giustiniano, M. ACS Org. Inorg. Au 2022, 2, 66. doi: 10.1021/acsorginorgau.1c00028
[27]	Zhang, J.; Xu, W.; Qu, Y.; Liu, Y.; Li, Y.; Song, H.; Wang, Q.; Chem. Commun. 2020, 56, 15212. doi: 10.1039/D0CC06645A
[28]	López-Mendoza, P.; Miranda, L. D. Org. Biomol. Chem. 2020, 18, 3487. doi: 10.1039/d0ob00136h pmid: 32347280
[29]	Yuan, Y.; Zhang, S.-Y.; Dong, W.-H.; Wu, F.; Xie, X.-M.; Zhang, Z.-G. Adv. Synth. Catal. 2021, 363, 4216. doi: 10.1002/adsc.202100474
[30]	Wei, J.; Gu, D.; Wang, S.; Hu, J.; Dong, X.; Sheng, R. Org. Chem. Front. 2018, 5, 2568. doi: 10.1039/C8QO00644J
[31]	Yuan, Y.; Dong, W.; Gao, X.; Gao, H.; Xie, X.; Zhang, Z. J. Org. Chem. 2018, 83, 2840. doi: 10.1021/acs.joc.7b03283 pmid: 29411608
[32]	Zhu, Z.-F.; Zhang, M.-M.; Liu, F. Org. Biomol. Chem. 2019, 17, 1531. doi: 10.1039/C8OB02786B
[33]	(a) Liu, W.; Ackermann, L. ACS Catal. 2016, 6, 3743. doi: 10.1021/acscatal.6b00993
	(b) Mukherjee, A.; Milstein, D. ACS Catal. 2018, 8, 11435. doi: 10.1021/acscatal.8b02869
	(c) Rohit, K. R.; Radhika, S.; Saranya, S.; Anilkumar, G. Adv. Synth. Catal. 2020, 362, 1602. doi: 10.1002/adsc.201901389
	(d) Cano, R.; Mackey, K.; McGlacken, G. P. Catal. Sci. Technol. 2018, 8, 1251. doi: 10.1039/C7CY02514A
	(e) Das, K.; Mondal, A.; Pal, D.; Srivastava, H. K.; Srimani, D. Organometallics 2019, 38, 1815. doi: 10.1021/acs.organomet.9b00131
	(f) Das, K.; Mondal, A.; Srimani, D. Chem. Commun. 2018, 54, 10582. doi: 10.1039/C8CC05877F
	(g) Das, K.; Mondal, A.; Srimani, D. J. Org. Chem. 2018, 83, 9553. doi: 10.1021/acs.joc.8b01316
[34]	Cheng, W.-M.; Shang, R. ACS Catal. 2020, 10, 9170. doi: 10.1021/acscatal.0c01979
[35]	Wang, L.; Ding, Q.; Li, X.; Peng, Y. Asian J. Org. Chem. 2019, 8, 385. doi: 10.1002/ajoc.201800733
[36]	Wei, W.; Bao, P.; Yue, H.; Liu, S.; Wang, L.; Li, Y.; Yang, D. Org. Lett. 2018, 20, 5291. doi: 10.1021/acs.orglett.8b02231 pmid: 30129769
[37]	Singh, M.; Yadav, A. K.; Yadav, L. D. S.; Singh, R. K. P. Synlett 2018, 29, 176. doi: 10.1055/s-0036-1590921
[38]	Lv, Y.; Bao, P.; Yue, H.; Li, J.-S.; Wei, W. Green Chem. 2019, 21, 6051. doi: 10.1039/C9GC03253C
[39]	Yang, W.; Li, B.; Zhang, M.; Wang, S.; Ji, Y.; Dong, S.; Feng, J.; Yuan, S. Chin. Chem. Lett. 2020, 31, 1313. doi: 10.1016/j.cclet.2019.10.022
[40]	Singh, H. K.; Kamal, A.; Kumari, S.; Maury, S. K.; Kushwaha, A. K.; Srivastava, V.; Singh, S. ChemistrySelect 2021, 6, 13982. doi: 10.1002/slct.202103548
[41]	Dahiya, A.; Das, B.; Sahoo, A. K.; Patel, B. K. Adv. Synth. Catal. 2022, 364, 966. doi: 10.1002/adsc.202101431
[42]	Liu, Y.; Kang, Y.; Wang, H.; Dong, Y.; Yang, T.; Wei, Q.; Jiang, Y.; Yang, Y.; Gao, H. Tetrahedron Lett. 2020, 61, 152348. doi: 10.1016/j.tetlet.2020.152348
[43]	(a) Jones, G. H.; Edwards, D. W.; Parr, D. A. J. Chem. Soc., Chem. Commun. 1976, 969.
	(b) West, J. G.; Huang, D.; Sorensen, E. J. Nat. Commun. 2015, 6, 10093. doi: 10.1038/ncomms10093
[44]	Singh, H. K.; Kamal, A.; Kumari, S.; Kumar, D.; Maury, S. K. Srivastava, V.; Singh, S. ACS Omega 2020, 5, 29854. doi: 10.1021/acsomega.0c03941
[45]	Santos, M. S.; Betim, H. L. I.; Kisukuri, C. M.; Delgado, J. A. C.; Corrêa, A. G.; Paixão, M. W. Org. Lett. 2020, 22, 4266. doi: 10.1021/acs.orglett.0c01297
[46]	(a) Zhou, Z.; Kong, X.; Liu, T. Chin. J. Org. Chem. 2021, 41, 3844. (in Chinese) doi: 10.6023/cjoc202106001
	( 周子杰, 孔祥梅, 刘天飞, 有机化学, 2021, 41, 3844.)
	(b) Gentry, E. C.; Knowles, R. R. Acc. Chem. Res. 2016, 49, 1546. doi: 10.1021/acs.accounts.6b00272
[47]	Liu, Y.; Chen, X.-L.; Li, X.-Y.; Zhu, S.-S.; Li, S.-J.; Song, Y.; Qu, L.-B.; Yu, B. J. Am. Chem. Soc. 2021, 143, 964. doi: 10.1021/jacs.0c11138
[48]	Gore, B. S.; Kuo, C.-Y.; Wang, J.-J. Chem. Commun. 2022, 58, 4087. doi: 10.1039/D2CC00717G
[49]	Cheung, K. P. S.; Sarkar, S.; Gevorgyan, V. Chem. Rev. 2022, 122, 1543. doi: 10.1021/acs.chemrev.1c00403
[50]	(a) Kunkely, H.; Vogler, A. J. Organomet. Chem. 1998, 559, 215. doi: 10.1016/S0022-328X(98)00411-2
	(b) Caspar, J. V. J. Am. Chem. Soc. 1985, 107, 6718. doi: 10.1021/ja00309a055
	(c) Harvey, P. D.; Gray, H. B. J. Am. Chem. Soc. 1988, 110, 2145. doi: 10.1021/ja00215a023
	(d) Harvey, P. D.; Schaefer, W. P.; Gray, H. B. Inorg. Chem. 1988, 27, 1101. doi: 10.1021/ic00279a034
	(e) Ohkubo, T.; Takao, K.; Tsubomura, T. Inorg. Chem. Commun. 2012, 20, 27.
	(f) Riese, S.; Holzapfel, M.; Schmiedel, A.; Gert, I.; Schmidt, D.; Wurthner, F.; Lambert, C. Inorg. Chem. 2018, 57, 12480. doi: 10.1021/acs.inorgchem.8b00974
[51]	Parasram, M.; Chuentragool, P.; Sarkar, D.; Gevorgyan, V. J. Am. Chem. Soc. 2016, 138, 6340. doi: 10.1021/jacs.6b01628 pmid: 27149524
[52]	Jia, X.; Zhang, Z.; Gevorgyan, V. ACS Catal. 2021, 11, 13217. doi: 10.1021/acscatal.1c04183

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