A New, Highly Selective, Free-Radical Aerobic Oxidation of Silanes to Silanols Catalysed by N-Hydroxyphthalimide under Mild Conditions.

Francesco Minisci; Francesco Recupero; Carlo Punta; Chiara Guidarini; Francesca Fontana; Gian Franco Pedulli

doi:10.1055/s-2002-32591

LETTER

A New, Highly Selective, Free-Radical Aerobic Oxidation of Silanes to Silanols Catalysed by N-Hydroxyphthalimide under Mild Conditions.

Francesco Minisci*^a, Francesco Recupero^a, Carlo Punta^a, Chiara Guidarini^a, Francesca Fontana^b, Gian Franco Pedulli^c
^a Dipartimento di Chimica, Materiali e Ingegneria Chimica ‘G.Natta’, Politecnico di Milano, via Mancinelli 7, 20131 Milano, Italy
Fax: +39(02)23993080; e-Mail: francesco.minisci@polimi.it;
^b Dipartimento di Ingegneria, Università di Bergamo, viale Marconi 5, 24044 Milano, Italy
^c Università di Bologna, Dipartimento di Chimica Organica ‘A.Mangini’, via S.Donato 15, 40127 Bologna BO, Italy

Abstract

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Abstract

Silanes are oxidised to silanols by molecular oxygen, under N-hydroxyphthalimide and Co(II) catalysis, under very mild conditions and in good yields and selectivity. The reaction proceeds through the superimposition of a redox chain to a free-radical chain reaction.

Key words

silanols - oxygen - N-hydroxyphthalimide - free radicals - chain reactions

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References

1 The Chemistry of Organic Silicon Compounds Part 1-3, Vol. 2: Rappoport Z. Apoloig V. Wiley; Chichester: 1998.

2 A review: Lickiss PD. Adv. Inorg. Chem. 1995, 42: 147

3 Hench LL. West JK. Chem. Rev. 1990, 90: 33

4 Mittal KL. Silanes and Other Coupling Agents VSP; Utrecht: 1992.

5 Nagai V. Honda K. Migita T. J. Organomet. Chem. 1967, 8: 372

6 Al-Shali SA. Eaborn C. Fatah FA. Najim ST. Chem. Commun. 1984, 318

7 Duffaut N. Calas R. Macé J. Bull. Soc. Chim Fr. 1959, 1971

8 Wiberg E. Amberger E. Hydrides of the Elements of Main Groups I-IV Elsevier; Amsterdam: 1971. p.523

9 Alexandrov YuA. Taumin BI. Russ. Chem. Rev. 1977, 46: 905

10 Adam W. Azzena H. Prechtl F. Hindahl K. Malish W. Chem. Ber. 1992, 125: 1409

11 Eaborn C. Organosilicon Compounds Butterworth; London: 1960. p.198

12 Ishii Y. Sakaguchi S. Iwahama T. Adv. Synth. Catal. 2001, 343: 393 ; a review

13 Minisci F. Punta C. Recupero F. Fontana F. Pedulli GF. Chem. Commun. 2002, 688

14 Walsh R. Acc. Chem. Res. 1981, 14: 246

15

Manuscript in preparation.

16

The evaluation of the rate constants for hydrogen abstraction by R₃SiOO· radical from >N-OH and by PINO radical from R₃Si-H is in progress.