washed four times with 15 mL of dichloromethane in a round-
bottomed flask under magnetic stirring. The filtered solution was
analyzed by means of GC and then evaporated under vacuum
at 0 ◦C.
4 (a) A. Lambert, J. A. Elings, D. J. Macquarrie, G. Carr and J. H.
Clark, Synlett., 2000, 7, 1052–1054; (b) J. A. Elings, R. Ait-Meddour,
J. H. Clark and D. J. Macquarrie, Chem. Commun., 1998, 2707–2708.
5 (a) W. Leitner, Acc. Chem. Res., 2002, 35, 746–756; (b) Chemical Syn-
thesis Using Supercritical Fluids, ed. P. Jessop, and W. Leitner, Wiley-
VCH, Weinheim-New-York, 1999; (c) S. Wells and J. M. DeSimone,
Angew. Chem. Int. Ed. Engl, 2001, 40, 519–527; (d) M. McHugh,
and V. J. Krukonis, Supercritical Fluid Extraction, Butterworth-
Heinemann, Boston, 1994.
Oxidation of adamantanone (1e) with silica-supported peracid
3 in dichloromethane. To a suspension of 0.05 g of 3
(0.7 mmol g-1, 0.035 mmol) in 1.5 mL of dichloromethane, 1 mL
of an equimolar 0.0175 M solution of adamantanone (1e) (with
adamantane as an internal standard) in dichloromethane was
added at once at room temperature under stirring. The reaction
was monitored by means of GC and the substrate conversion
was determined from the integrals of the peaks corresponding
to the substrate 1e and the internal standard.
6 (a) R. T. Baker, S. Kobayashi and W. Leitner, Adv. Synth. Catal.,
2006, 348, 1337–1340; (b) W. Leitner, Pure Appl. Chem., 2004, 76,
635–644; (c) J. R. Hyde, P. Licence, D. Carter and M. Poliakoff, Appl.
Catal. A, 2001, 222, 119–121.
7 (a) See for instance:Z. Hou, N. Theyssen, A. Brinkmann, K. V.
Klementiev, W. Gruener, M. Buehl, W. Schmidt, B. Spliethoff, B.
Tesche, C. Weidenthaler and W. Leitner, J. Catal., 2008, 258, 315–323;
(b) F. Zayed, L. Greiner, P. S. Schulz, A. Lapkin and W. Leitner, Chem.
Commun., 2008, 79–81; (c) Z. Hou, N. Theyssen and W. Leitner, Green
Chem., 2007, 9, 127–132; (d) M. I. Burguete, A. Cornejo, E. Garc´ıa-
Verdugo, M. J. Gil, S. V. Luis, J. A. Mayoral, V. Mart´ınez-Merino
and M. Sokolova, J. Org. Chem., 2007, 72, 4344–4350; (e) P. Clark,
M. Poliakoff and A. Wells, Adv. Synth. Catal., 2007, 349, 2655–2659;
(f) G. A. Leeke, R. C. D. Santos, B. Al-Duri, J. P. K. Seville, C. J.
Smith, C. K. Y. Lee, A. B. Holmes and I. F. McConvey, Org. Proc.
Res. Dev., 2007, 11, 144–148; (g) P. Stephenson, B. Kondor, P. Licence,
K. Scovell, S. K. Ross and M. Poliakoff, Adv. Synth. Catal., 2006,
348, 1605–1610; (h) M. E. Gonza´lez-Nu´n˜ez, R. Mello, A. Olmos, R.
Acerete and G. Asensio, J. Org. Chem., 2006, 71, 1039–1042; (i) J.-Q.
Wang, D.-L. Kong, J.-Y. Chen, F. Cai and L.-N. He, J. Mol. Catal. A,
2006, 249, 143–148; (j) Z. Hou, N. Theyssen, A. Brinkmann and W.
Leitner, Angew. Chem., Int. Ed. Engl., 2005, 44, 1346–1349; (k) P. B.
Webb, T. E. Kunene and D. J. Cole-Hamilton, Green Chem., 2005,
7, 373–379; (l) J. R. Hyde, B. Walsh, J. Singh and M. Poliakoff,
Green Chem., 2005, 7, 357–361; (m) J. R. Hyde, B. Walsh and M.
Poliakoff, Angew. Chem., Int. Ed. Engl., 2005, 44, 7588–7591; (n) Y.
Kokubo, A. Hasegawa, S. Kuwata, K. Ishihara, H. Yamamoto and T.
Ikariya, Adv. Synth. Catal., 2005, 347, 220–224; (o) C. K. Y. Lee, A. B.
Holmes, S. V. Ley, I. F. McConvey, B. Al-Duri, G. A. Leeke, R. C. D.
Santos and J. P. K. Seville, Chem. Commun., 2005, 2175–2177; (p) P.
Licence, W. K. Gray, M. Sokolova and M. Poliakoff, J. Am. Chem.
Soc., 2005, 127, 293–298; (q) P. Stephenson, P. Licence, S. K. Ross
and M. Poliakoff, Green Chem., 2004, 6, 521–523; (r) M. T. Reetz and
W. Wiesenho¨fer, Chem. Commun., 2004, 2750–2751; (s) M. T. Reetz,
W. Wiesenhoefer, G. Francio and W. Leitner, Adv. Synth. Catal.,
2003, 345, 1221–1228; (t) P. B. Webb, M. F. Sellin, T. E. Kunene,
S. Williamson, A. M. Z. Slawin and D. J. Cole-Hamilton, J. Am.
Chem. Soc., 2003, 125, 15577–15588; (u) J DeSimone, M. Selva and
P. Tundo, J. Org. Chem., 2001, 66, 4047–4049; (v) N. J. Meehan, M.
Poliakoff, A. J. Sandee, J. N. H. Joost, P. C. J. Kamer and P. W. N. M.
vanLeeuwen, Chem. Commun., 2000, 1497–1498; (w) W. K. Gray,
F. R. Smail, M. G. Hitzler, S. K. Ross and Poliakoff, J. Am. Chem.
Soc., 1999, 121, 10711–10718; (x) M. G. Hitzler, F. R. Smail, S. K.
Ross and M. Poliakoff, Chem. Commun., 1998, 359–360.
Oxidation of adamantanone (1e) with m-CPBA. To 1 mL
of an equimolar 0.0175 M solution of adamantanone (1e)
(adamantane as an internal standard) in dichloromethane,
1.5 mL of a 0.023 M solution of 98% m-CPBA were added
at once at room temperature under stirring. The reaction
was monitored through GC and the substrate conversion was
determined from the integrals of the peaks corresponding to the
substrate 1e and the internal standard.
Acknowledgements
Financial support from the Spanish Direccio´n General de
Investigacio´n, CTQ2007–65251/BQU and Consolider Ingenio
2010 (CSD2007–00006), is gratefully acknowledged. AO thanks
the Spanish Ministerio de Educacio´n y Ciencia for a fellowship.
We thank Solvay Qu´ımica S.L. for a generous gift of 70%
hydrogen peroxide. We also thank the SCSIE (Universidad
de Valencia) for allowing us access to their instruments and
facilities.
Notes and references
1 (a) C. Jime´nez-Sanchidria´n and J. R. Ruiz, Tetrahedron, 2008, 64,
2011–2026; (b) M. Mihovilovic, F. Rudroff and B. Groetzl, Curr. Org.
Chem., 2004, 8, 1057–1069; (c) Bolm C. Palazzi, and O. Beckmann,
in Transition Metals for Organic Synthesis, ed. M. Beller, and
C. Bolm, Wiley-VCH, Weinheim, 2004, p. 267-274; (d) M. Renz and
B. Meunier, Eur. J. Org. Chem., 1999, 4, 737–750; (e) G. Strukul,
Angew. Chem., Int. Ed. Engl., 1998, 37, 1199–1209; (f) G. R. Krow,
Org. React., 1993, 43, 251–798.
2 (a) M. Boronat, P. Concepcio´n, A. Corma and M. Renz, Catal.
Today, 2007, 121, 39–44; (b) M. D. Mihovilovic, Curr. Org. Chem.,
2006, 10, 1265–1287; (c) G.-J. Brink, I. W. C. E. Arends and R. A.
Sheldon, Chem. Rev., 2004, 104, 4105–4123; (d) C. Bolm, C. Palazzi,
G. Franzio` and W. Leitner, Chem. Commun., 2002, 1588–1589.
3 (a) M. E. Gonza´lez-Nu´n˜ez, R. Mello, A. Olmos and G. Asensio,
J. Org. Chem., 2006, 71, 6432–6436; (b) M. E. Gonza´lez-Nu´n˜ez, R.
Mello, A. Olmos and G. Asensio, J. Org. Chem., 2005, 70, 10879–
10882; (c) P. J. Kropp, G. W. Breton, J. D. Fields, J. C. Tung and B. R.
Loornis, J. Am. Chem. Soc., 2000, 122, 4280–4285; (d) J. D. Fields
and P. J. Kropp, J. Org. Chem., 2000, 65, 5937–5941.
8 (a) R. E. Montgomery, J. Am. Chem. Soc., 1974, 96, 7820–7821;
(b) J. O. Edwards, R. H. Pater, R. Curci and F. Di Furia, Photochem.
Photobiol., 1979, 30, 63–70; (c) R. Curci, M. Fiorentino, L. Troisi,
J. O. Edwards and R. H. Pater, J. Org. Chem., 1980, 45, 4758–4760;
(d) A. R. Gallopo and J. O. Edwards, J. Org. Chem., 1981, 46, 1684–
1688.
9 H.-H. G. Tsai, G.-L. Jheng and H.-M. Kao, J. Am. Chem. Soc., 2008,
130, 11566–11567.
10 R. Mello, A. Olmos, T. Varea and M. E. Gonzalez-Nunez, Anal.
´
´ ˜
Chem., 2008, 80, 9355–9359.
11 D. D. Perrin, W. L. F. Armarego, Purification of Laboratory
Chemicals, 3rd edn, Pergamon, New York, 1988.
This journal is
The Royal Society of Chemistry 2009
Green Chem., 2009, 11, 994–999 | 999
©