Subscribe to RSS
DOI: 10.1055/a-2350-1323
Silylium-Ion-Initiated Twofold Halodealkylation of Fully Alkylated Silanes
T. R. thanks the Fonds der Chemischen Industrie for a predoctoral fellowship (Kekulé scholarship, 2024–2026). Generous funding by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under Germany’s Excellence Strategy (EXC 2008/1 – 390540038, UniSysCat) is gratefully acknowledged. M.O. is indebted to the Einstein Foundation Berlin for an endowed professorship.
Abstract
The synthesis of silanes starting from multifunctionalized precursors often suffers from low chemoselectivity due to the similar kinetic reaction profiles, leading to the formation of difficult to separate side products. The opposite approach, which is an access based on unreactive tetraalkylsilanes as starting materials, is far less developed. Making use of the silylium-ion-initiated chemoselective halodealkylation of tetraalkylsilanes recently developed by our laboratory, an extension of this protocol, namely the direct synthesis of dihalosilanes from tetraalkylsilanes, is reported. Following a sequence of halodehydrogenation and halodealkylation, trialkylhydrosilanes can also be converted into dihalosilanes. Commercially available 1,2-dihaloethane acts as the halogen source and is involved in the generation of the catalytically active arenium ion by an SEAr substitution of the benzene solvent. The formation of an uncommon halogen-substituted silylium ion as an intermediate is assumed, likely accounting for the need of an elevated reaction temperature.
Key words
arenium ions - halodealkylation - halodehydrogenation - Lewis acids - silicon - silylium ionsSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-2350-1323.
- Supporting Information
Publication History
Received: 05 June 2024
Accepted after revision: 21 June 2024
Accepted Manuscript online:
21 June 2024
Article published online:
19 July 2024
© 2024. Thieme. All rights reserved
Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany
-
References
- 1a Rochow EG. J. Am. Chem. Soc. 1945; 67: 963
- 1b Zhang Y, Li J, Liu H, Ji Y, Zhong Z, Su F. ChemCatChem 2019; 11: 2757
- 1c Zhang P, Zhang D, Dong J, Chen G, Li J. Org. Process Res. Dev. 2022; 26: 2270
- 2 Arkles B. In Handbook of Grignard Reagents . Silverman GS, Rakita PE. Marcel Dekker; New York: 1996: 667-675
- 3 He T, Klare HF. T, Oestreich M. Nature 2023; 623: 538
- 4 For a chemoselective demethylation with a hypervalent iodine reagent, see: Matsuoka K, Komami N, Kojima M, Mita T, Suzuki K, Maeda S, Yoshino T, Matsunaga S. J. Am. Chem. Soc. 2021; 143: 103
- 5 Conceptual work: Klare HF. T, Oestreich M. J. Am. Chem. Soc. 2021; 143: 15490
- 6a Klare HF. T, Albers L, Süsse L, Keess S, Müller T, Oestreich M. Chem. Rev. 2021; 121: 5889
- 6b Walker JC. L, Klare HF. T, Oestreich M. Nat. Chem. Rev. 2020; 4: 54
- 7 Moretto H.-H, Schulze M, Wagner G. In Ullmann’s Encyclopedia of Industrial Chemistry . Wiley-VCH; Weinheim: 2000: 675-708
- 8a Chen Q.-A, Klare HF. T, Oestreich M. J. Am. Chem. Soc. 2016; 138: 7868
- 8b Wu Q, Irran E, Müller R, Kaupp M, Klare HF. T, Oestreich M. Science 2019; 365: 168
- 9 Bartlett PD, Condon FE, Schneider A. J. Am. Chem. Soc. 1944; 66: 1531
- 10 Lehmann M, Schulz A, Villinger A. Angew. Chem. Int. Ed. 2009; 48: 7444
- 11 Merk A, Bührmann L, Kordts N, Görtemaker K, Schmidtmann M, Müller T. Chem. Eur. J. 2021; 27: 3496
- 12 Wu Q, Qu Z.-W, Omann L, Irran E, Klare HF. T, Oestreich M. Angew. Chem. Int. Ed. 2018; 57: 9176
- 13 He T, Klare HF. T, Oestreich M. ACS Catal. 2021; 11: 12186
- 14a Reed CA. Acc. Chem. Res. 2010; 43: 121
- 14b Wu Q, Roy A, Irran E, Qu Z.-W, Grimme S, Klare HF. T, Oestreich M. Angew. Chem. Int. Ed. 2019; 58: 17307
- 15 Harris RK, Becker ED, Cabral de Menezes SM, Goodfellow R, Granger P. Solid State Nucl. Magn. Reson. 2002; 22: 458
- 16 Naganawa Y, Sakamoto K, Nakajima Y. Org. Lett. 2020; 23: 601
- 17 Iwata A, Toyoshima Y, Hayashida T, Ochi T, Kunai A, Ohshita J. J. Organomet. Chem. 2003; 667: 90
- 18 Kunai A, Sakurai T, Toyoda E, Ishikawa M, Yamamoto Y. Organometallics 1994; 13: 3233
- 19 Out GJ. J, Klok H.-A, Schwegler L, Frey H, Möller M. Macromol. Chem. Phys. 1995; 196: 185
- 20 Li L, Li Y, Wang H, Liu S, Bao JJ. Colloids Surf. A 2019; 570: 322
- 21 Belyakova ZV, Chernyshev EA, Storozhenko PA, Knyazev SP, Turkel’taub GN, Parshina EV, Kisin AV. Russ. J. Gen. Chem. 2006; 76: 925
- 22 Asuke T, West R. J. Inorg. Organomet. Polym. 1994; 4: 45
- 23a Wrobel D, Tacke R, Wannagat U, Harder U. Chem. Ber. 1982; 115: 1694
- 23b Schraml J, Chvalovský V, Mägi M, Lippmaa E. Collect. Czech. Chem. Commun. 1979; 44: 854
- 24 Enthaler S. J. Appl. Polym. Sci. 2015; 132: 41287
- 25 Lee H.-J, Kwak C, Kim D.-P, Kim H. Green Chem. 2021; 23: 1193
For reviews of silylium ions, see: