D
Y.-q. Yuan et al.
Letter
Synlett
(5) Field, L. D.; Messerle, B. A.; Rehr, M.; Soler, L. P.; Hambley, T. W.
Organometallics 2003, 22, 2387.
TBHP
(6) Sridhar, M.; Raveendra, J.; Ramanaiah, B. C.; Narsaiah, C. Tetra-
hedron Lett. 2011, 52, 5980.
I
HO-I
[Si]-OR
(7) (a) Purkayashtha, A.; Baruah, J. B. J. Mol. Catal. A: Chem. 2003,
198, 47. (b) Mirza-Aghayan, M.; Boukherroub, R.; Bolourtchian,
M. J. Organomet. Chem. 2005, 690, 2372.
[Si]
H
[Si]
I
(8) Purkayashtha, A.; Baruah, J. B. Silicon Chem. 2002, 1, 229.
(9) (a) Blakwell, J. M.; Foster, K. L.; Beck, V. H.; Piers, W. E. J. Org.
Chem. 1999, 64, 4887. (b) Kim, Y.; Chang, S. Angew. Chem. Int.
Ed. 2016, 55, 218.
R-OH
H2O
Scheme 3 Proposed mechanism for the alkoxysilane synthesis
(10) Gao, D.; Cui, C. Chem. Eur. J. 2013, 19, 11143.
(11) (a) Toutov, A. A.; Betz, K. N.; Haibach, M. C.; Romine, A. M.;
Grubbs, R. H. Org. Lett. 2016, 18, 5776. (b) Bideau, F. L.; Coradin,
T.; Hénique, J.; Samuel, E. Chem. Commun. (Cambridge) 2001,
1408.
(12) Tanabe, Y.; Okumura, H.; Maeda, A.; Murakami, M. Tetrahedron
Lett. 1994, 35, 8413.
(13) (a) Liu, C.; Zhang, H.; Shi, W.; Lei, A. Chem. Rev. 2011, 111, 1780.
(b) Yeung, C. S.; Dong, V. M. Chem. Rev. 2011, 111, 1215. (c) Shi,
W.; Liu, C.; Lei, A. Chem. Soc. Rev. 2011, 40, 2761. (d) Song, G.;
Wang, F.; Li, X. Chem. Soc. Rev. 2012, 41, 3651. (e) Li, B.-J.; Shi,
Z.-J. Chem. Soc. Rev. 2012, 41, 5588.
alkoxylated silane derivatives in the absence of any ligand,
base, or metal. The method features readily available start-
ing materials, an environmentally benign oxidant, and tran-
sition-metal-free characteristics. The extended scope of
this reaction is under investigation, and the results will be
discussed in due course.
Acknowledgment
(14) (a) Wang, L.; Zhu, H.; Guo, S.; Cheng, J.; Yu, J.-T. Chem. Commun.
(Cambridge) 2014, 50, 10864. (b) Xu, L.; Zhang, S.; Li, P. Org.
Chem. Front. 2015, 2, 459. (c) Leifert, D.; Studer, A. Org. Lett.
2015, 17, 386. (d) Zhang, L.; Liu, D.; Liu, Z.-Q. Org. Lett. 2015, 17,
2534. (e) Gu, J.; Cai, C. Chem. Commun. (Cambridge) 2016, 52,
10779. (f) Zhang, L.; Hang, Z.; Liu, Z.-Q. Angew. Chem. 2016, 128,
244.
This work was supported by the Natural Science Foundation of Zheji-
ang Province P. R. of China (No. Y16B020018) and the Public Welfare
Technology Application Foundation of Lishui (2014JYZB49).
Supporting Information
Supporting information for this article is available online at
(15) (a) Guo, S.; Yuan, Y.; Xiang, J. Org. Lett. 2013, 15, 4654. (b) Yuan,
Y.; Guo, S.; Xiang, J. Synlett 2013, 24, 443. (c) Guo, S.; He, W.;
Xiang, J.; Yuan, Y. Tetrahedron Lett. 2014, 55, 6407. (d) Guo, S.;
He, W.; Xiang, J.; Yuan, Y. Chem. Commun. (Cambridge) 2014, 50,
8578. (e) Guo, S.; Yuan, Y.; Xiang, J. New J. Chem. 2015, 39, 3093.
(f) Guo, S.; Yuan, Y. Synlett 2015, 26, 1961.
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References
(1) (a) Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic
Synthesis, 3rd ed.; Wiley: New York, 1999. (b) Huang, C.;
Ghavtadze, N.; Chattopadhyay, B.; Gevorgyan, V. J. Am. Chem.
Soc. 2011, 133, 17630. (c) Herrera, N. N.; Letoffe, J.-M.; Putaux,
J.-L.; David, L.; Bourgeat-Lami, E. Langmuir 2004, 20, 1564.
(d) Brook, M. Silicon in Organic, Organometallic, and Polymer
Chemistry; Wiley: New York, 2000.
(2) For selected examples, see: (a) Studer, A.; Bossart, M.; Vasella, T.
Org. Lett. 2000, 2, 985. (b) Behloul, C.; Guijarro, D.; Yus, M. Tetra-
hedron 2005, 61, 6908. (c) López, R.; Zalacain, M.; Palomo, C.
Chem. Eur. J. 2011, 17, 2450. (d) Dias, L. C.; de Lucca, E. C. Jr.;
Ferreira, M. A. B.; Garcia, D. C.; Tormena, C. F. J. Org. Chem. 2012,
77, 1765. (e) Poulsen, P. H.; Santos Feu, K.; Matos Paz, B.; Jensen,
F.; Jørgensen, K. A. Angew. Chem. Int. Ed. 2015, 54, 8203.
(3) (a) Do, Y.; Han, J.; Rhee, Y. H.; Park, J. Adv. Synth. Catal. 2011,
353, 3363. (b) Toh, C. K.; Poh, H. T.; Lim, C. S.; Fan, W. Y.
J. Organomet. Chem. 2012, 717, 9.
(16) (a) Shang, X.; Liu, Z.-Q. Org. Biomol. Chem. 2016, 14, 7829.
(b) Toutov, A. A.; Liu, W.-B.; Betz, K. N.; Fedorov, A.; Stoltz, B. M.;
Grubbs, R. H. Nature 2015, 518, 80. (c) Weickgenannt, A.;
Oestreich, M. Chem. Asian J. 2009, 4, 406.
(17) NH4I-Catalyzed Oxidative Dehydrocoupling of Silanes with
Alcohols: General Procedure
70% aq TBHP (4.0 mmol) was added dropwise over 10 min to a
solution of the appropriate silane (1.0 mmol) and NH4I (0.20
mmol) in the appropriate alcohol (1 mL), and the mixture was
stirred at r.t. until the reaction was complete (TLC). The reaction
was then quenched with sat. aq Na2S2O3, and the mixture was
washed with brine, extracted with EtOAc, dried (Na2SO4), and
concentrated under vacuum. The crude product was purified by
column chromatography (silica gel, PE).
Ethoxy(triphenyl)silane (3aa)
Colorless liquid; yield: 280 mg (92%). 1H NMR (300 MHz, CDCl3):
δ = 7.66 (d, J = 6.4 Hz, 6 H), 7.42 (dt, J = 13.5, 6.6 Hz, 9 H), 3.90 (q,
J = 7.0 Hz, 2 H), 1.26 (t, J = 6.9 Hz, 3 H). 13C NMR (75 MHz,
CDCl3): δ = 135.49, 134.55, 130.06, 127.95, 59.85, 18.49. HRMS
(TOF, EI+): m/z calcd for C20H20OSi: 304.1283; found: 304.1285.
(4) Toh, C. K.; Sum, Y. N.; Fong, W. K.; Ang, S. G.; Fan, W. Y. Organo-
metallics 2012, 31, 3880.
© Georg Thieme Verlag Stuttgart · New York — Synlett 2017, 28, A–D