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DOI: 10.1055/a-2675-3935
Iron Catalyst and Blue Light Partnership for Selective Desulfurization of Secondary and Primary Thioamides
Supported by: National Research Agency ANR-22-PESP-0006
Funding Information This work benefited from State aid managed by the National Research Agency under France 2030 with the reference “ANR-22-PESP-0006”. Q.Z. thanks the China Scholarship Council for a PhD fellowship.

Dedication
In honor of Prof. Paul Knochel’s 70th birthday and for his incredible creativity, dynamism, and inspiration.
Abstract
Commercially available iron(0) Fe2(CO)9 precatalyst can promote the selective desulfurization of secondary and primary carboxamides leading to the corresponding secondary amines and nitriles, respectively. The reaction is conducted under hydrosilylation conditions using phenylsilane or diethylsilane and blue LED irradiation (2 × 24 W, 450–460 nm) at ambient conditions.
Keywords
Iron catalysis - Desulfurization - Hydrosilylation; Secondary thioamide - Primary thioamide - Blue lightPublication History
Received: 20 June 2025
Accepted after revision: 03 August 2025
Accepted Manuscript online:
04 August 2025
Article published online:
01 September 2025
© 2025. Thieme. All rights reserved.
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References
- 1a Mahanta N, Szantai-Kis DM, Petersson EJ, Mitchell DA. ACS Chem Biol 2019; 14: 142
- 1b Hansen TN, Olsen CA. Chem Eur J 2024; 30: e202303770
- 2a Corsaro A, Pistara A. Tetrahedron 1998; 54: 15027
- 2b Masuda R, Hojo M, Ichi T, Sasano S, Kobayashi T, Kuroda C. Tetrahedron Lett 1991; 32: 1195
- 2c Rani RR, Rahman MF, Bhalerao UT. Tetrahedron 1953; 1992: 48
- 2d Mavassagh B, Lakouraj MM, Ghodrati K. Synth Commun 2000; 30: 2353
- 2e Mohammadpoor-Baltork I, Sadeghi MM, Esmayilpour K. Synth Commun 2003; 33: 953
- 2f Baltork IM, Khodaei M, Nikoofar K. Tetrahedron Lett 2003; 44: 591
- 2g Shibahara F, Suenami A, Yoshida A, Murai T. Chem Commun 2007; 2354
- 2h Bahrami K, Khodaei MM, Shakibaian V, Khaledian D, Yousefi BH. J Sulfur Chem 2012; 33: 155
- 2i Das P, Das P, Mondal S, Ray S. ChemistrySelect 2024; 9: e202303973
- 3a Raucher S, Klein P. Tetrahedron Lett 1980; 21: 4061
- 3b Sundberg RJ, Walters CP, Bloom JD. J Org Chem 1981; 46: 3730
- 3c Ghattas A-BAG, Jorgensen KA, Lawesson SO. Acta Chem Scand B 1982; 36: 505
- 4a Kornfeld EC. J Org Chem 1951; 16: 131
- 4b Hurd CD, Rudner B. J Am Chem Soc 1951; 73: 5157
- 4c Cronyn MW, Goodrich JE. J Am Chem Soc 1952; 74: 3936
- 5 Yu Y-J, Zhang F-L, Cheng J, Hei J-H, Deng W-T, Wang Y-F. Org Lett 2018; 20: 24
- 6 Luo J, Rauch M, Avram L, Ben-David Y, Milstein D. J Am Chem Soc 2020; 142: 21628
- 7 Wang Z, Chen S, Chen C, Yang Y, Wang C. Angew Chem Int Ed 2023; 62: e202215963
- 8a Zhang M, Zhang A. Appl Organomet Chem 2010; 24: 751
- 8b Addis D, Das S, Junge K, Beller M. Angew Chem Int Ed 2011; 50: 6004
- 8c Obligacion J-V, Chirik PJ. Nat Rev Chem 2018; 2: 15
- 8d Shaikh NS. ChemistrySelect 2019; 4: 6753
- 8e Bhunia M, Sreejyothi P, Mandal SW. Coord Chem Rev 2020; 405: 213110
- 8f de Almeida LD, Wang H, Junge K, Cui X, Beller M. Angew Chem Int Ed 2021; 60: 550
- 9 Nad P, Goswami S, Kisan HK, Mukherjee A. Chem Eur J 2025; 31: e202500738
- 10a Junge K, Schröder K, Beller M. Chem Commun 2011; 47: 4849
- 10b Le Bailly BAF, Thomas SP. RSC Adv 2011; 1: 1435
- 10c Mérel DS, Do MLT, Gaillard S, Dupau P, Renaud J-L. Coord Chem Rev 2015; 288: 50
- 10d Misal Castro LC, Li H, Sortais J-B, Darcel C. Green Chem 2015; 17: 2283
- 10e Guo N, Zhu SF. Chin J Org Chem 2015; 35: 1383
- 10f Bauer I, Knölker H-J. Chem Rev 2015; 115: 3170
- 10g Lopes R, Royo B. Isr J Chem 2017; 57: 1151
- 10h Wei D, Darcel C. Chem Rev 2019; 119: 2550
- 10i Wei D, Netkaew C, Darcel C. Eur J Inorg Chem 2019; 2471
- 10j Rana S, Biswas JP, Paul S, Paik A, Maiti D. Chem Soc Rev 2021; 50: 243
- 10k Wu J, Darcel C. Adv Synth Catal 2023; 365: 948
- 11a Fukumoto K, Sakai A, Oya T, Nakazawa H. Chem Commun 2012; 48: 3809
- 11b Fukumoto K, Sakai A, Hayasaka K, Nakazawa H. Organometallics 2013; 32: 2889
- 11c Fukumoto K, Sakai A, Murai T, Nakazawa H. Heteroat Chem 2014; 25: 607
- 12 Zhang Q, Darcel C. Eur J Org Chem 2025; e202500048
- 13a Bézier D, Venkanna GT, Sortais J-B, Darcel C. ChemCatChem 2011; 3: 1747
- 13b Bézier D, Venkanna GT, Misal Castro LC. et al. Adv Synth Catal 1879; 2012: 354
- 13c Misal Castro LC, Li H, Sortais J-B, Darcel C. Chem Commun 2012; 48: 10514
- 13d Li H, Misal Castro LC, Zheng J. et al. Angew Chem Int Ed 2013; 52: 8045
- 13e Quintero-Duque S, Li H, Misal Castro LC. et al. Isr J Chem 2017; 57: 1216
- 13f Wei D, Netkaew C, Carré V, Darcel C. ChemSusChem 2019; 12: 3008
- 13g Wei D, Netkaew C, Darcel C. Adv Synth Catal 2019; 361: 1781
- 13h Wei D, Netkaew C, Wu J, Darcel C. ChemCatChem 2020; 12: 5449
- 13i Wu J, Tongdee S, Ammaiyappan Y, Darcel C. Adv Synth Catal 2021; 363: 3859
- 13j Wu J, Narayanasamy SN, Darcel C. Chem Eur J 2023; 15: e202300963
- 13k Zhang Q, Darcel C. Eur J Org Chem 2024; e202400475
- 14a Avalos M, Babiano R, Duran CJ, Jimenez JL, Palacios JC. Tetrahedron Lett 1994; 35: 477
- 14b Avalos M, Babiano R, Cintas P. et al. Tetrahedron 1997; 53: 14463
- 15a Lim M-I, Ren W-Y, Klein RS. J Org Chem 1982; 47: 4594
- 15b Subbas Bose D, Jayalaksmi B, Goud PR. Synthesis 1999; 1724
- 16 Yamagushi K, Yajima K, Mizuno N. Chem Commun 2012; 48: 11247
- 17 Gopi E, Gravel E, Doris E. Eur J Org Chem 2019; 4043
- 18 Murata Y, Iwasa H, Matsumura M, Yasuike S. Chem Pharm Bull 2020; 68: 679
- 19 Suzuki H, Tani H, Takeuchi S. Bull Chem Soc Jpn 1985; 58: 2421
- 20 Aso Y, Omote K, Takagi S, Otsubo T, Ogura F. J Chem Res Synop 1995; 4: 152
- 21 Gopi E, Geertsen V, Gravel E, Doris E. ChemCatChem 2019; 11: 5758
- 22 Mineno T, Takebe Y, Chiaki C, Mashimo S. Int J Org Chem 2014; 4: 169
- 23 Xu T, Cao T, Feng Q, Huang S, Liao S. Chem Commun 2020; 56: 5151
- 24a Qian X-Y, Li S-Q, Song J, Xu H-C. ACS Catal 2017; 7: 2730-2734
- 24b Xu Z-M, Li H-X, Young DJ, Zhu D-L, Li H-Y, Lang J-P. Org Lett 2019; 21: 237
- 24c Guo Y, Chang R, Fu Z, Zhou C-Y, Guo Z. Green Chem 2023; 25: 5206
- 25 Simons RS, Galat KJ, Bradshaw JD. et al. J Organomet Chem 2001; 628: 241
- 26 Simons RS, Tessier CA. Organometallics 1996; 15: 2604
- 27 Corriu RJP, Lanneau GF, Chauhan BPS. Organometallics 2001; 1993: 12
- 28 Alper H, Chan ASK. Inorg Chem 1974; 13: 225
- 29 Zhou S, Addis D, Das S, Junge K, Beller M. Chem Commun 2009; 4883
- 30 Hanada S, Ishida T, Motoyama Y, Nagashima H. J Org Chem 2007; 72: 7551
- 31 Song H, Xiao Y, Zhang Z. et al. J Org Chem 2022; 87: 790
- 32 Ma Z, Zhou B, Li X. et al. Chem Sci 2022; 13: 111
- 33 Konishi H, Tanaka H, Manabe K. Org Lett 2017; 19: 1578
- 34 Cheng C, Brookhart M. J Am Chem Soc 2012; 134: 11304
- 35 Guria S, Hassan MMM, Dey S, Singh KN, Chattopadhyay B. Angew Chem Int Ed 2024; 63: e202409010
- 36 Dong S, Zong Z, Sun N. et al. New J Chem 2023; 47: 5603
- 37 Li Y, Dong Y, Li Y. Chin J Org Chem 2024; 44: 638
For selected reviews on the use of thioamides, see:
For a representative review on oxidative desulfurization of thioamides to amides, see:
For selective recent examples, see:
For representative examples of reduction of thioamides using stoichiometric metal hydride reagents, see:
For representative examples of reduction of thioamides using Raney Nickel, see:
For selected general reviews dealing with selectivity in catalyzed hydrosilylation, see:
For representative reviews on iron catalysts in reduction area, see:
For representative examples, see: