Abstract
Methylenation of (3R,6R)-2-(4-X-benzylidene)-6-isopropyl-3-methylcyclohexanones (X = F, Cl, Ph) with dimethylsulfoxonium methylide occurs stereoselectively to give 1(S)-(4-X-phenyl)-5(R)-isopropyl-8(R)-methyl-3(R)-spiro[2.5]octanones, whose stereochemistry was established by 1H NMR spectroscopy. The configuration of the chiral centers in the cyclohexanone fragment and its preferred conformation (methyl is axial and isopropyl is equatorial) in the products do not change with respect to the starting enones. The mutual trans-arrangement of the carbonyl and aryl groups at the newly formed three-membered ring was established; the aryl group also occupies the trans-position with respect to the axial methyl group of the cyclohexanone fragment. Using methylenation of the compound with X = Ph as an example, a mixture of by-products resulting from oxidative hydroxylation at the α-position relative to the carbonyl group was isolated. The resulting chiral spiro[2.5]octanones induce a helical supramolecular ordering in the nematic mesophase of 4-pentyl-4′-cyanobiphenyl and exhibit a twisting power only somewhat (by 20–30%) lower than the starting enones.
Similar content being viewed by others
References
L. A. Kutulya, Nonlinear Optics of Liquid and Photorefractive Crystals II, Proc. SPIE, 1998, 3488, 84.
L. A. Kutulya, in Funktsional’nye materialy dlya nauki i tekhniki [Functional Materials for Science and Engineering], Ed. V. P. Seminozhenko, Inst. of Single Crystals, Kharkov, 2001, 381 (in Russian).
S. N. Yarmolenko, L. A. Kutulya, V. V. Vashchenko, and L. V. Chepeleva, Liq. Cryst., 1994, 16, 877.
S. N. Yarmolenko, L. V. Chepeleva, L. A. Kutulya, V. V. Vashchenko, T. G. Drushlyak, and O. A. Ponomarev, Zh. Obshch. Khim., 1995, 65, 145 [Russ. J. Gen. Chem., 1995, 65 (Engl. Transl.)].
V. V. Vashchenko, L. A. Kutulya, M. N. Pivnenko, and N. I. Shkol’nikova, Izv. Akad. Nauk. Ser. Khim., 2003, 2276 [Russ. Chem. Bull., Int. Ed., 2003, 52, 2406].
N. I. Boiko, L. A. Kutulya, Yu. A. Reznikov, T. A. Sergan, and V. P. Shibaev, Mol. Cryst. Liq. Cryst., 1994, 251, 311.
P. Van De Witte, J. C. Galan, and J. Lub, Liq. Cryst., 1998, 24, 819.
A. Yu. Bobrovsky, N. I. Boiko, and V. P. Shibaev, Liq. Cryst., 1998, 25, 393.
L. A. Kutulya, S. N. Yarmolenko, V. V. Vashchenko, L. V. Chepeleva, L. D. Patsenker, and O. A. Ponomarev, Zh. Fiz. Khim., 1995, 69, 88 [Russ. J. Phys. Chem., 1995, 69 (Engl. Transl.)].
B. V. Trost and L. S. Melvin, Sulfur Ylides, Emerging Synthetic Intermediates, Academic Press, New York, 1975.
Yu. G. Gololobov, A. N. Nesmeyanov, L. P. Lysenko, and I. E. Boldeskul, Tetrahedron, 1975, 43, 2609.
J. A. Donnelly, D. D. Keane, K. G. Marathe, D. C. Meaney, and E. M. Phuilbin, Chem. Ind., 1967, 1402.
P. Bennett, J. A. Donnelly, D. C. Meaney, and P. Oboyle, J. Chem. Soc., Perkin Trans. 1, 1972, 1554.
D. J. Collins, G. D. Falon, and C. E. Skene, Aust. J. Chem., 1992, 45, 71.
T. E. Jacks, H. Nibbe, and D. F. Wieme, J. Org. Chem., 1993, 58, 4584.
L. A. Kutulya, N. S. Pivnenko, I. B. Nemchenok, T. V. Khandrimaidova, G. P. Semenkova, V. I. Biba, and V. G. Tishchenko, Zhurn. Obshch. Khim., 1987, 57, 397 [J. Gen. Chem. USSR, 1987, 57 (Engl. Transl.)].
N. S. Pivnenko, V. V. Vashchenko, L. A. Kutulya, A. O. Doroshenko, and L. V. Chepeleva, Izv. Akad. Nauk. Ser. Khim., 2001, 1519 [Russ. Chem. Bull., Int. Ed., 2001, 50, 1596].
H. Gunter, NMR Spectroscopy. An Introduction, J. Wiley and Sons, Chichester-New York-Brisbane-Toronto, 1980.
S. Klod and E. Kleinpeter, J. Chem. Soc., Perkin Trans. 2, 2001, 1893.
C. A. G. Haasnoot, F. A. A. M. Leeuw, and C. Altona, Tetrahedron, 1980, 36, 2783.
R. J. Abraham, Progress in NMRS, 1999, 35, 85.
C. W. Haigh and R. B. Mallion, Org. Magn. Reson., 1972, 4, 203.
R. J. Abraham and M. Reid, J. Chem. Soc., Perkin Trans. 2, 2002, 1081.
R. J. Abraham, M. Mobli, and R. J. Smith, Magn. Reson. Chem., 2003, 41, 26.
R. J. Abraham and N. J. Ainger, J. Chem. Soc., Perkin Trans. 2, 1999, 441.
J. March, Advanced Organic Chemistry: Reactions, Mechanisms, and Structure, 4th ed., Wiley-Interscience-J. Wiley and Sons, New York-Chichester-Brisbane-Toronto-Singapore, 1992, 1495 pp.
A. I. Krivoshey, L. A. Kutulya, N. I. Shkolnikova, and N. S. Pivnenko, Proc. XVI Int. School-Seminar “Spectroscopy of Molecules and Crystals”, SPIE Proc., 2004, 5507, 249.
L. A. Kutulya, A. I. Krivoshei, N. S. Pivnenko, and N. I. Shkol’nikova, Zhurn. Struktur. Khim., 2004, 45, 419 [Russ. J. Struct. Chem., 2004, 45 (Engl. Transl.)].
L. A. Kutulya, D.Sc. Thesis (Chemistry), Bogatsky Physico-Chemical Institute, National Academy of Sciences of Ukraine, Odessa, 1993, 461 pp. (in Russian).
N. I. Shkol’nikova, Ph.D Thesis (Chemistry), Inst. Single Crystals, National Academy of Sciences of Ukraine, Kharkov, 2003, 139 pp. (in Russian).
L. A. Kutulya, L. D. Patsenker, V. V. Vashchenko, V. P. Kuznetsov, V. I. Kulishov, Yu. N. Surov, and V. V. Kravets, Izv. Akad. Nauk. Ser. Khim., 1995, 1247 [Russ. Chem. Bull., 1995, 44, 1200 (Engl. Transl.)].
L. Kutulya, V. Vashchenko, G. Semenkova, and N. Shkolnikova, Mol. Cryst. Liq. Cryst., 1999, 331, 583.
P. Kassubek and G. Maier, Mol. Cryst. Liq. Cryst., 1969, 8, 305.
L. A. Kutulya, G. P. Semenkova, S. N. Yarmolenko, A. P. Fedoryako, I. E. Novikova, and L. D. Patsenker, Kristallografiya, 1993, 38, 183 [Sov. Phys.-Crystallogr., 1993, 38 (Engl. Transl.)].
Author information
Authors and Affiliations
Additional information
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2331–2341, October, 2005.
Rights and permissions
About this article
Cite this article
Gella, I.M., Pivnenko, N.S., Kutulya, L.A. et al. New chiral spiro[2.5]octanones as products of methylenation of (3R, 6R)-2-arylidene-6-isopropyl-3-methylcyclohexanones with dimethylsulfoxonium methylide. Synthesis, stereochemistry, and behavior in liquid-crystalline systems. Russ Chem Bull 54, 2406–2416 (2005). https://doi.org/10.1007/s11172-006-0130-5
Received:
Revised:
Issue Date:
DOI: https://doi.org/10.1007/s11172-006-0130-5