I. Shevchenko, A. Rogalyov, A. B. Rozhenko, G.-V. Röschenthaler
FULL PAPER
maining after evaporation of hexane afforded 50 mg of a white
product. M.p. 164–165 °C. 1H NMR (CDCl3): δ = 1.3–1.9 (m, 8 [1] H. J. Bestmann, R. Zimmermann, in Organic Phosphorus Com-
pounds (Eds.: G. M. Kosolapoff, L. Maier), Wiley-Interscience,
New York, 1976, vol. 3, chapter 5a.
[2] D. Bourissou, O. Guerret, F. P. Gabbai, G. Bertrand, Chem.
Rev. 2000, 100, 39–91.
[3] N. Kuhn, J. Fahl, D. Blaser, R. Boese, Z. Anorg. Allg. Chem.
1999, 625, 729.
[4] O. I. Kolodiazhnyi, Phosphorus Ylides, Wiley-VCH, Weinheim,
New York, Chichester, Brisbane, Singapore, Toronto, 1999.
[5] a) I. Shevchenko, V. Andrushko, E. Lork, G.-V. Röschenthaler,
Eur. J. Inorg. Chem. 2003, 54–56; b) I. Shevchenko, V. And-
rushko, E. Lork, G.-V. Röschenthaler, Eur. J. Inorg. Chem.
2002, 2985–2990.
[6] Y. Canac, S. Conejero, M. Soleilhavoup, B. Donnadieu, G. Ber-
trand, J. Am. Chem. Soc. 2006, 128, 459–464.
[7] Only a nitrile ylide substituted with an adamantyl group is
known to be stable in crystalline form at room temperature:
E. P. Janulis, S. R. Willson, A. J. Arduengo III, Tetrahedron
Lett. 1984, 25, 405.
H), 2.20 (s, 6 H, Me), 2.28 (s, 3 H, Me), 2.90 (m, 1 H),, 3.38 (m, 1
H), 6.87 (br. s, 2 H, Ar) ppm. 13C NMR (CDCl3): δ = 20.03 (br.
s), 20.35 (s), 20.51 (s), 20.67 (s), 21.47 (s), 39.90 (s), 52.93 (s), 85.25
1
1
(m), 123.63 (q, JF,C = 284 Hz, CF3), 124.50 (q, JF,C = 284 Hz,
CF3), 128.76 (s), 128.85 (s), 130.79 (s), 134.34 (br. s), 135.80 (br.
s), 138.71 (s), 190.64 (s) ppm. 19F NMR (CDCl3): δ = –67.56 (q,
4
4JF,F = 10.2 Hz, 3 F), –73.80 (q, JF,F = 10.2 Hz, 3 F) ppm. MS
(APCI): m/z 378 [M + H]+.
The same product was obtained when ylide 4, obtained as de-
scribed above (together with Ph3PO), was heated in cyclohexene at
75 °C for 6 h.
Compounds 10 and 11: PhNCO (0.8 mL) was added to a reaction
solution of ylide 4 obtained from acylimine 12 (50 mg) and tri-
phenylphosphane (100 mg) in thf (0.8 mL) as described above and
the mixture was heated at 60 °C for 10 h. The 19F NMR spectrum
showed almost quantitative formation of the isomers 10 and 11 (δ
= –72.7 and –74.0 ppm, respectively; both 6 F), which were isolated
chromatographically as described previously.[13]
[8] D. G. Gilheany, in The Chemistry of Organophosphorus Com-
pounds, vol. 3 (Ed.: F. R. Hartley), John Wiley & Sons, Chich-
ester, UK, 1994, p. 1–44.
[9] J. Albanbauer, K. Burger, E. Burgis, D. Marquarding, L.
Schabl, I. Ugi, Justus Liebigs Ann. Chem. 1976, 36–53.
[10] D. V. Griffiths, J. C. Tebby, J. Chem. Soc., Chem. Commun.
1986, 871–872.
When a solution of ylide 7 in CDCl3 was heated at 55 °C in the
presence of PhNCO the yield of compounds 10 and 11 was sub-
stantially lower (about 20%). The main process in this case is an
addition reaction between PhNCO and ylide 4. This product will
be described in a subsequent paper.
[11] S. Fergus, S. J. Eustace, A. F. Hegarty, J. Org. Chem. 2004, 69,
4663–4669.
[12] K. Burger, K. Einhellig, G. Süss, A. Gieren, Angew. Chem. Int.
Ed. Engl. 1973, 12, 156–157.
Computational Details: All of the structures were fully optimised
without symmetry constraints. The BP86 functional[14,15] with an
approximate treatment of the electronic Coulomb interaction [reso-
lution of identity (RI)[16] algorithm] and the triple-zeta valence
(TZV) quality basis sets[17] implemented in the TURBOMOLE
program set[18] was used for the geometry optimisation. One set of
polarisation functions was added for all atoms (the standard TZVP
basis sets included in the TURBOMOLE packet). An SCF conver-
gence criterion SCFConv = 1.0ϫ10–8 Hartree and the finest grid
value (grid = 5) was used in the optimisation. All the structures
were proved to be local minima in energy; the vibration analyses
were performed by computing analytical first- and second-order
derivatives.[19] A full account of the optimised geometries is given
in the Supporting Information. The VMD program packet[20] was
used for the graphical presentation of the calculated structures.
[13] K. Burger, H. Goth, W. Höhenberger, Chem. Ztg. 1977, 101,
453–454.
[14] A. D. Becke, Phys. Rev. A 1988, 38, 3098–3100.
[15] J. P. Perdew, Phys. Rev. B 1986, 33, 8822–8824.
[16] a) B. I. Dunlap, J. W. Conolly, J. R. Sabin, J. Chem. Phys. 1979,
71, 3396–3402; b) O. Vahtras, J. Almlöf, M. W. Feyereisen,
Chem. Phys. Lett. 1993, 213, 514–518; K. Eichkorn, O.
Treutler, H. Öhm, M. Häser, R. Ahlrichs, Chem. Phys. Lett.
1995, 240, 283–289.
[17] A. Schaefer, C. Huber, R. Ahlrichs, J. Chem. Phys. 1994, 100,
5829–5835.
[18] R. Ahlrichs, M. Bär, M. Häser, H. Horn, C. Kölmel, Chem.
Phys. Lett. 1989, 162, 165–169; R. Ahlrichs, M. v. Arnim, in
Methods and Techniques in Computational Chemistry MET
ECC-95 (Eds.: E. Clementi, G. Corongiu), STEF, Cagliari,
Chemistry/main_turbomole.html.
[19] P. Deglmann, F. Furche, R. Ahlrichs, Chem. Phys. Lett. 2002,
362, 511–518; P. Deglmann, F. Furche, J. Chem. Phys. 2002,
117, 9535–9538.
Acknowledgments
[20] VMD for WIN-32, Version 1.8.2 (December 4, 2003): W. Hum-
phrey, A. Dalke, K. Schulten, J. Mol. Graphics 1996, 14, 33–
38.
We thank Professor W. W. Schoeller at the University of Bielefeld
for access to the TURBOMOLE program set. Financial support
by the Deutsche Forschungsgemeinschaft (DFG) (436 UKR 113/
58/0-1) is gratefully acknowledged (I. S.)
Received: June 20, 2006
Published Online: October 27, 2006
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