Synlett 2017; 28(13): 1620-1623
DOI: 10.1055/s-0036-1588816
letter
© Georg Thieme Verlag Stuttgart · New York

Metal-Free Ammonium Iodide Catalyzed Oxidative Dehydrocoupling of Silanes with Alcohols

Yan-qin Yuan
Department of Chemistry, Lishui University, Lishui, 323000, P. R. of China   Email: paillasanthosh@gmail.com   Email: guosr9609@lsu.edu.cn
,
Pailla Santhosh Kumar*
Department of Chemistry, Lishui University, Lishui, 323000, P. R. of China   Email: paillasanthosh@gmail.com   Email: guosr9609@lsu.edu.cn
,
Sheng-rong Guo*
Department of Chemistry, Lishui University, Lishui, 323000, P. R. of China   Email: paillasanthosh@gmail.com   Email: guosr9609@lsu.edu.cn
› Author Affiliations
Further Information

Publication History

Received: 14 February 2017

Accepted after revision: 02 April 2017

Publication Date:
17 May 2017 (online)


Abstract

An ammonium iodide catalyzed direct oxidative coupling of silanes with alcohols to give various alkoxysilane derivatives was discovered. tert-Butyl hydroperoxide proved to be an efficient oxidant for this transformation. Attractive features of this protocol include its transition-metal-free nature and the mild reaction conditions.

Supporting Information

 
  • References

    • 1a Greene TW. Wuts PG. M. Protective Groups in Organic Synthesis . 3rd ed. Wiley; New York: 1999
    • 1b Huang C. Ghavtadze N. Chattopadhyay B. Gevorgyan V. J. Am. Chem. Soc. 2011; 133: 17630
    • 1c Herrera NN. Letoffe J.-M. Putaux J.-L. David L. Bourgeat-Lami E. Langmuir 2004; 20: 1564
    • 1d Brook M. Silicon in Organic, Organometallic, and Polymer Chemistry. Wiley; New York: 2000

      For selected examples, see:
    • 2a Studer A. Bossart M. Vasella T. Org. Lett. 2000; 2: 985
    • 2b Behloul C. Guijarro D. Yus M. Tetrahedron 2005; 61: 6908
    • 2c López R. Zalacain M. Palomo C. Chem. Eur. J. 2011; 17: 2450
    • 2d Dias LC. de Lucca EC. Jr. Ferreira MA. B. Garcia DC. Tormena CF. J. Org. Chem. 2012; 77: 1765
    • 2e Poulsen PH. Santos Feu K. Matos Paz B. Jensen F. Jørgensen KA. Angew. Chem. Int. Ed. 2015; 54: 8203
    • 3a Do Y. Han J. Rhee YH. Park J. Adv. Synth. Catal. 2011; 353: 3363
    • 3b Toh CK. Poh HT. Lim CS. Fan WY. J. Organomet. Chem. 2012; 717: 9
  • 4 Toh CK. Sum YN. Fong WK. Ang SG. Fan WY. Organometallics 2012; 31: 3880
  • 5 Field LD. Messerle BA. Rehr M. Soler LP. Hambley TW. Organometallics 2003; 22: 2387
  • 6 Sridhar M. Raveendra J. Ramanaiah BC. Narsaiah C. Tetrahedron Lett. 2011; 52: 5980
    • 7a Purkayashtha A. Baruah JB. J. Mol. Catal. A: Chem. 2003; 198: 47
    • 7b Mirza-Aghayan M. Boukherroub R. Bolourtchian M. J. Organomet. Chem. 2005; 690: 2372
  • 8 Purkayashtha A. Baruah JB. Silicon Chem. 2002; 1: 229
    • 9a Blakwell JM. Foster KL. Beck VH. Piers WE. J. Org. Chem. 1999; 64: 4887
    • 9b Kim Y. Chang S. Angew. Chem. Int. Ed. 2016; 55: 218
  • 10 Gao D. Cui C. Chem. Eur. J. 2013; 19: 11143
    • 11a Toutov AA. Betz KN. Haibach MC. Romine AM. Grubbs RH. Org. Lett. 2016; 18: 5776
    • 11b Bideau FL. 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
    • 14a Wang L. Zhu H. Guo S. Cheng J. Yu J.-T. Chem. Commun. (Cambridge) 2014; 50: 10864
    • 14b Xu L. Zhang S. Li P. Org. Chem. Front. 2015; 2: 459
    • 14c Leifert D. Studer A. Org. Lett. 2015; 17: 386
    • 14d Zhang L. Liu D. Liu Z.-Q. Org. Lett. 2015; 17: 2534
    • 14e Gu J. Cai C. Chem. Commun. (Cambridge) 2016; 52: 10779
    • 14f Zhang L. Hang Z. Liu Z.-Q. Angew. Chem. 2016; 128: 244
    • 16a Shang X. Liu Z.-Q. Org. Biomol. Chem. 2016; 14: 7829
    • 16b Toutov AA. Liu W.-B. Betz KN. Fedorov A. Stoltz BM. Grubbs RH. Nature 2015; 518: 80
    • 16c 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.