Mn(CO)₅Br-Catalyzed Hydrosilation of Alkene with Hydrosiloxanes and Hydrogen-Containing Silicone Oil

Abstract

A cyano-ligand-assisted Mn(CO)₅Br-catalyzed hydrosilylation of alkenes with 1,1,1,3,3-pentamethyldisiloxane (PMDS) was developed. This versatile manganese catalyst proved broadly applicable, delivering anti-Markovnikov products with high regioselectivity. Furthermore, the catalytic system was also successfully applied to the functionalization of hydrogen-containing silicone oil. The desired product organosilicon oil was characterized by thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR), and gel permeation chromatography (GPC).

Keywords

Manganese catalyst - Hydrosilylation - Organosilicon oil - Hydrogen-containing silicone oil - Anti-Markovnikov regioselectivity

Publikationsverlauf

Eingereicht: 28. November 2025

Angenommen nach Revision: 29. Dezember 2025

Accepted Manuscript online:
29. Dezember 2025

Artikel online veröffentlicht:
15. Januar 2026

• References

• 1 Franz AK, Wilson SO. J Med Chem 2013; 56: 388-405
• 2 Marciniec B, Maciejewski H. Perspectives of Hydrosilylation Reactions. Cham: Springer; 2023
• 3 Marciniec B. Hydrosilylation: A Comprehensive Review on Recent Advances. Dordrecht: Springer; 2009
• 4 Sanchez C, Belleville P, Popall M, Nicole L. Chem Soc Rev 2011; 40: 696-753
• 5 Atienza CCH, Tondreau AM, Weller KJ. et al. ACS Catal 2012; 2: 2169-2172
• 6 Obligacion JV, Chirik PJ. Nat Rev Chem 2018; 2: 15-34
• 7 Lewis LN, Stein J, Gao Y, Colborn RE, Hutchins G. Platin Met Rev 1997; 41: 66-75
• 8 Zhao Y, Guo C, Wu H. Prog Chem 2014; 26: 345-357
• 9 Marciniec B. Comprehensive Handbook on Hydrosilylation. Amsterdam: Elsevier; 2013
• 10 Benkeser RA, Kang J. J Organomet Chem 1980; 185: C9-C12
• 11 Pan Z, Liu M, Zheng C, Gao D, Huang W. Chin J Chem 2017; 35: 1227-1230
• 12 Trovitch RJ, Lobkovsky E, Chirik PJ. J Am Chem Soc 2006; 128: 2552-2553
• 13 Speier JL. In: Advances in Organometallic Chemistry. Stone FGA, West R. eds. New York: Academic Press; 1979
• 14 Nakamura E, Sato K. Nat Mater 2011; 10: 158-161
• 15 Wang L, Li Y, Li Q. et al. J Catal 2025; 116554
• 16 Bocian A, Skrodzki M, Kubicki M, Pietraszuk C. Appl Catal, A 2020; 602: 117665
• 17 Yu Z, Song Z, Lu C, Zhang D, Wang B, He Y. Appl Organomet Chem 2022; 36: e6648
• 18 Huang M, Zhou X, Shao Y, Zhou Y, Zhu S, Zhu S-F. J Catal 2023; 428: 115197
• 19 Li L-J, He Y, Yang Y, Zhang X, Tung C-H, Wang W. CCS Chem 2024; 6: 537-584
• 20 Sunada Y, Noda D, Soejima H, Tsutsumi H, Nagashima H. Organometallics 2015; 34: 2896-2906
• 21 Noda D, Tahara A, Sunada Y, Nagashima H. J Am Chem Soc 2016; 138: 2480-2483
• 22 Buslov I, Song F, Hu X. Angew Chem Int Ed 2016; 55: 12483-12487
• 23 Sanagawa A, Nagashima H. Organometallics 2018; 37: 2859-2871
• 24 Ito T, Sunada Y. Org Process Res Dev 2023; 27: 1203-1209
• 25 Gilani SH, Alibhai Y. J Toxicol Environ Health Part A 1990; 30: 23-31
• 26 Committee for Medicinal Products for Human Use. Guideline on the Specification Limits for Residues of Metal Catalysts or Metal Reagents. London: European Medicines Agency; 2008
• 27 Dong J, Yuan XA, Yan Z, Xie J, Zhu Q, Zeng X. Nat Chem 2021; 13: 182-190
• 28 Goncharova IK, Filatov SA, Drozdov AP. et al. J Catal 2024; 429: 115269
• 29 Vivien A, Veyre L, Mirgalet R, Camp C, Thieuleux C. Chem Commun 2022; 58: 4091-4094
• 30 Vivien A, Veyre L, Mirgalet R, Camp C, Thieuleux C. Green Chem 2023; 25: 7721-7728
• 31 Yang X, Wang C. Chin J Chem 2018; 36: 1047-1051
• 32 Yang X, Wang C. Angew Chem Int Ed 2018; 57: 923-928
• 33 Li Q, Huo S, Meng L, Li X. Cat Sci Technol 2022; 12: 2649-2658
• 34 Chen M-Y, Soulé N, Zuluaga A. et al. ACS Catal 2025; 15: 16840-16850
• 35 Studzińska S, Buszewski B. J Sep Sci 2012; 35: 1123-1131
• 36 Sugiura M, Kobayashi S, Hagio H. ChemInform. 2005 36.
• 37 Żak P, Bołt M, Kubicki M, Pietraszuk C. Dalton Trans 2018; 47: 1903-1910
• 38 Anoshkin VI, Kovalev IF, Khudobin YI, Kharitonov NP, Voronkov MG. Izv Akad Nauk SSSR, Ser Khim 1980; 2: 86-95