Communication
ChemComm
intrinsically more difficult to epoxidise than (cyclic) cis-alkenes
T. Ooi and K. Maruoka, Angew. Chem., Int. Ed., 2007, 46, 4222;
J. W. Steed and J. L. Atwood, Supramolecular Chemistry., John Wiley
and the ring opening of the products to diols (the only by-
&
Sons, Chichester, UK, 2009; R. Breslow and L. E. Overman, J. Am.
8
,9
product) is, in these cases, facilitated due to steric reasons.
Chem. Soc., 1970, 92, 1075; S. Beckendorf, S. Asmus and O. Garc ´ı a
Manche n˜ o, ChemCatChem, 2012, 4, 926.
C. L. Liotta and H. P. Harris, J. Am. Chem. Soc., 1974, 96, 2250;
E. V. Dehmlow, Angew. Chem., Int. Ed., 1977, 16, 493; P. Viout, J. Mol.
Catal., 1981, 10, 231; J.-F. Bri `e re, S. Oudeyer, V. Dalla and
V. Levacher, Chem. Soc. Rev., 2012, 41, 1696.
Even though the overall performance obtained with the SIP
catalysts is lower than that of known molecular epoxidation
2
3
À1
catalysts such as MTO (TOFmax = 39 000 h for cyclooctene as
9
,14–16
substrate at 0 1C),
the SIPs exhibit the advantage of being
D. J. Sam and H. E. Simmons, J. Am. Chem. Soc., 1972, 94, 4024.
more stable and recyclable; at 70 1C the catalytically active
1
6
4 G. De Faveri, G. Ilyashenko and M. Watkinson, Chem. Soc. Rev.,
011, 40, 1722; R. H. Ingle and N. K. K. Raj, J. Mol. Catal. A: Chem.,
2 2
species formed from MTO and H O decomposes rapidly.
2
It is noteworthy that the epoxidation of allyl alcohol leads to
a good conversion, yet low selectivity. This is likely due to the
good miscibility of the epoxide product in water, which leads to
over-oxidation and the formation of glycerol. Also, the SIPs
catalyse the epoxidation of propene to propene oxide (PO).
Although the conversion is low, it should be noted that there
are only a few reports on propene epoxidation using molecular
2008, 294, 8; M. B ¨o sing, A. N o¨ h, I. Loose and B. Krebs, J. Am. Chem.
Soc., 1998, 120, 7252; K. Sato, M. Aoki and R. Noyori, Science, 1998,
281, 1646.
5
M. C. A. van Vliet, I. W. C. E. Arends and R. A. Sheldon, J. Chem. Soc.,
Perkin Trans. 1, 2000, 377.
6 D. Mandelli, M. C. A. van Vliet, U. Arnold, R. A. Sheldon and
U. Schuchardt, J. Mol. Catal. A: Chem., 2001, 168, 165; D. Veljanovski,
A. Sakthivel, W. A. Herrmann and F. E. K u¨ hn, Adv. Synth. Catal., 2006,
348, 1752.
5
catalysts, all of which display similar conversions. In this case,
7 I. I. E. Markovits, W. A. Eger, S. Yue, M. Cokoja, C. J. M u¨ nchmeyer,
B. Zhang, M.-D. Zhou, A. Genest, J. Mink, S.-L. Zang, N. R o¨ sch and
F. E. K u¨ hn, Chem. – Eur. J., 2013, 19, 5972.
S. Huber, M. Cokoja and F. E. K u¨ hn, J. Organomet. Chem., 2014,
751, 25.
although the catalytic performance of the SIP is lower than that
of MTO, the system presented here is recyclable and so the SIPs
outcompete MTO in the long term.
The transfer of the perrhenate anion into a hydrophobic
medium enhances its supramolecular interactions, resulting in
8
9
1
S. A. Hauser, M. Cokoja and F. E. K u¨ hn, Catal. Sci. Technol., 2013, 3, 552.
0 D. Betz, A. Raith, M. Cokoja and F. E. K u¨ hn, ChemSusChem, 2010,
, 559.
3
very robust and active catalysts for biphasic alkene epoxidation 11 E. A. Katayev, G. V. Kolesnikov and J. L. Sessler, Chem. Soc. Rev.,
2
009, 38, 1572; M. Saeki, Y. Sasaki, A. Nakai, A. Ohashi, D. Banerjee,
by hydrogen peroxide. This is the first report on the epoxidation
of alkenes catalysed by perrhenate in organic solvents and
exploits the concept of transferring compounds regarded as
notoriously inactive in catalysis into an organic phase to
significantly enhance catalytic performance. Furthermore, the
back-transfer of the anion allows for straightforward separation
A. C. Scheinost and H. Foerstendorf, Inorg. Chem., 2012, 51, 5814.
2 R. J. Ellis, J. Chartres, D. K. Henderson, R. Cabot, P. R. Richardson,
F. J. White, M. Schr ¨o der, J. R. Turkington, P. A. Tasker and K. C.
Sole, Chem. – Eur. J., 2012, 18, 7715; J. R. Turkington, P. J. Bailey,
J. B. Love, A. M. Wilson and P. A. Tasker, Chem. Commun., 2013,
1
49, 1891; A. M. Wilson, P. J. Bailey, P. A. Tasker, J. R. Turkington,
R. A. Grant and J. B. Love, Chem. Soc. Rev., 2014, 43, 123.
and recovery of the catalyst, which clearly outperforms other 13 J. R. Turkington, V. Cocalia, K. Kendall, C. A. Morrison, P. Richardson,
T. Sassi, P. A. Tasker, P. J. Bailey and K. C. Sole, Inorg. Chem., 2012,
immobilized molecular catalysts, so offering a simple, sustainable
alternative to established molecular catalysts.
51, 12805.
1
4 I. I. E. Markovits, M. H. Anthofer, H. Kolding, M. Cokoja, A. P o¨ thig,
A. Raba, W. A. Herrmann, R. Fehrmann and F. E. K u¨ hn, Catal. Sci.
Technol., 2014, 4, 3845.
5 H.-J. Lee, T.-P. Shi, D. H. Busch and B. Subramaniam, Chem. Eng.
Sci., 2007, 62, 7282.
Notes and references
1
1
M. Raynal, P. Ballester, A. Vidal-Ferran and P. W. N. M. van Leeuwen,
Chem. Soc. Rev., 2014, 43, 1660; M. Raynal, P. Ballester, A. Vidal- 16 P. Altmann, M. Cokoja and F. E. K u¨ hn, Eur. J. Inorg. Chem., 2012,
Ferran and P. W. N. M. van Leeuwen, Chem. Soc. Rev., 2014, 43, 1734;
K. Brak and E. N. Jacobsen, Angew. Chem., Int. Ed., 2013, 52, 534;
3235–3239; F. E. K u¨ hn, A. Scherbaum and W. A. Herrmann,
J. Organomet. Chem., 2004, 689, 4149.
Chem. Commun.
This journal is ©The Royal Society of Chemistry 2015