L. Monnereau, D. Sémeril, D. Matt
FULL PAPER
formation of the linear aldehyde is the preferred formation and 2 and the complexes 3 and 4 were prepared according to litera-
ture procedures.[
23]
with 2-vinylnaphthalene of an alkyl intermediate (Figure 2),
rather than an allyl-type complex (of type A, Scheme 3), the General Procedure for the Hydroformylation Experiments: The hy-
latter coordination mode being prevented by strong steric droformylation experiments were carried out in a glass-lined,
1
00 mL stainless steel autoclave containing a magnetic stirring bar.
interactions between the naphthyl fragment of the substrate
and the pocket that hosts the metal. Our findings are a fur-
ther confirmation that metal confinement may induce shape
selectivity.
In a typical run, the autoclave was charged under nitrogen with
Rh(acac)(1,3-calix-diphosphite)] (0.002 mmol) in olefin solution,
[
free 1,3-calix-diphosphite dissolved in olefin (total amount of ole-
fin: 10 mmol), and internal standard (decane, 0.5 mL), when re-
quired. Once closed, the autoclave was flushed twice with syngas
2 2
(CO:H = 1:1, v/v), pressurised with a CO:H (1:2 or 1:1) mixture
and heated. At the end of the run, the autoclave was cooled to
room temperature before being depressurised. A sample was taken
1
and analysed by GC or by H NMR spectroscopy.
Acknowledgments
The authors wish to thank the French Agence Nationale de la Re-
cherche (ANR) for financial support (ANR-MATCALCAT fund-
ing scheme). The University of Strasbourg is gratefully acknowl-
edged for a grant to L. M. (Bourse Présidence).
Figure 2. Favorable and unfavorable intermediates in the hydro-
formylation of 2-vinylnaphthalene.
[
[
1] Rhodium Catalyzed Hydroformylation (Eds.: P. W. M.
van Leeuwen, C. Claver), Kluwer, Dordrecht, 2000.
2] J. Falbe, Carbon Monoxyde in Organic Synthesis, Springer,
Berlin, 1970.
3] F. J. Smith, Platinum Met. Rev. 1975, 19, 93–95.
4] R. L. Pruett, J. A. Smith, U. S. Patent 3,527,809 to Union Car-
bide 1970.
[
[
Conclusions
The hydroformylation of non-functionalised α-olefins
is efficiently catalysed in the absence of solvents by
[
[
5] R. L. Pruett, Ann. N. Y. Acad. Sci. 1977, 295, 239–248.
6] R. Fowler, H. Connor, R. A. Baehl, Chemtech 1976, 772–772.
[
Rh(acac)(“1,3-calix-diphosphite”)] complexes. It was [7] R. Fowler, H. Connor, R. A. Baehl, Hydrocarbon Proc. 1976,
55, 247–249.
shown that in all cases the reaction rate is considerably in-
creased with respect to reactions performed in toluene.
Furthermore, the catalysts display a high selectivity for lin-
ear aldehydes (except for allyl benzyl ether), a result which
[
[
8] E. A. V. Brewester, Chem. Eng. 1976, 83, 90–91.
9] C. P. Casey, G. T. Whiteker, M. G. Melville, L. M. Petrovich,
J. A. Gavney Jr., D. R. Powell, J. Am. Chem. Soc. 1992, 114,
5535–5543.
indicates that the ability of the hemispherical ligands to em- [10] P. W. N. M. van Leeuwen, P. C. J. Kamer, J. N. H. Reek, P. Di-
erkes, Chem. Rev. 2000, 100, 2741–2769.
11] P. C. J. Kamer, P. W. N. M. van Leeuwen, J. N. H. Reek, Acc.
Chem. Res. 2001, 34, 895–904.
brace the catalytic centre are not affected by the substrates
[
studied nor by combinations of the latter with the aldehydes
formed. A remarkable result was obtained in the hydrofor-
mylation of 1-octene with catalyst 3, which resulted in a
[
12] M.-N. Birkholz, Z. Freixa, P. W. N. M. van Leeuwen, Chem.
Soc. Rev. 2009, 38, 1099–1118.
–1
[13] R. Paciello, L. Siggel, M. Röper, Angew. Chem. Int. Ed. 1999,
TOF as high as 17290 mol(converted 1-octene)·mol(Rh) ·
–
1
38, 1920–1923.
h , the linear aldehyde selectivity being 97.9% in this case.
[
14] L. A. van der Veen, P. C. J. Kamer, P. W. N. M. van Leeuwen,
Angew. Chem. Int. Ed. 1999, 38, 336–338.
was dissolved in toluene (c = 0.7 ), this rate corresponds [15] L. A. van der Veen, P. H. Keeven, G. C. Schoemaker, J. N. H.
In comparison with our earlier study, in which the olefin
to an eightfold acceleration. Further studies on the rhodium
catalysts presented in this work will focus on their possible
recycling as well their use in domino reactions involving a
hydroformylation step.
Reek, P. C. J. Kamer, P. W. N. M. van Leeuwen, M. Lutz, A. L.
Spek, Organometallics 2000, 19, 872–883.
[
16] W. Ahlers, M. Röper, P. Hofmann, D. C. M. Warth, R. Paciello,
WO 01/58589 (BASF) 2001.
[
[
17] J. R. Briggs, G. T. Whiteker, Chem. Commun. 2001, 2174–2175.
18] R. P. J. Bronger, P. C. J. Kamer, P. W. N. M. van Leeuwen, Or-
ganometallics 2003, 22, 5358–5369.
[
19] A. van Rooy, P. C. J. Kamer, P. W. N. M. van Leeuwen, K.
Goubitz, J. Fraanje, N. Veldman, A. L. Spek, Organometallics
1996, 15, 835–847.
20] L. A. van der Veen, P. C. J. Kamer, P. W. N. M. van Leeuwen,
Organometallics 1999, 18, 4765–4777.
Experimental Section
General Methods: All syntheses were performed in Schlenk-type
[
flasks under dry nitrogen. Solvents were dried by conventional
1
methods and were distilled immediately prior to use. Routine H
[
21] J. I. van der Vlugt, R. Sablong, P. C. M. M. Magusin, A. M.
Mills, A. L. Spek, D. Vogt, Organometallics 2004, 23, 3177–
NMR spectra (used in the determination of some conversions and
1
selectivities) were recorded by using a Bruker AVANCE 300. H
3183.
NMR spectra were referenced to residual protonated solvents (δ =
[
22] D. Sémeril, C. Jeunesse, D. Matt, L. Toupet, Angew. Chem. Int.
3
7.26 ppm for CDCl ). The catalytic solutions were analysed by
Ed. 2006, 45, 5810–5814.
using a Varian 3900 gas chromatograph equipped with a WCOT
fused-silica column (25 mϫ0.25 mm). 1,3-Calix-diphosphites 1
[23] D. Sémeril, D. Matt, L. Toupet, Chem. Eur. J. 2008, 14, 7144–
7155.
3072
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