Chemistry Of Unique Chiral Olefins. 1. Synthesis, Enantioresolution, Circular Dichroism, And Theoretical Determination Of The Absolute Stereochemistry Of Trans- And Cis-1,1',2,2',3,3',4,4'-octahydro-4,4'-biphenanthrylidenes
作者： Nobuyuki Harada , Akira Saito , Nagatoshi Koumura , Hisashi Uda , Ben de Lange
DOI: 10.1021/JA970667U
关键词: Configuration interaction 、 Dipole 、 Stereochemistry 、 Molecular orbital 、 Chiral stationary phase 、 Circular dichroism 、 Spectral line 、 High-performance liquid chromatography 、 Enantiomer 、 Chemistry
摘要: Unique chiral olefins, (E)-1,1‘,2,2‘,3,3‘,4,4‘-octahydro-4,4‘-biphenanthrylidene (1) and its (Z)-isomer 2, were synthesized. When these compounds are directly enantioresolved by using the HPLC Okamoto column with a stationary phase, optically pure enantiomers obtained. The CD spectra of olefins exhibit very intense Cotton effects in 1Bb transition region reflecting their strongly twisted π-electron systems. UV (M,M)-(E)-1 (M,M)-(Z)-2 theoretically calculated self-consistent field/configuration interaction/dipole velocity molecular orbital method. From calculation results, absolute stereostructures determined to be [CD(+)239.0]-(M,M)-(E)-1 [CD(+)238.1]-(M,M)-(Z)-2, respectively.
acs.org
core.ac.uk
narcis.nl参考文章(20)
Nobuyuki Harada, Hisashi Uda, Tetsuo Nozoe, Yoshio Okamoto, Hidetsugu Wakabayashi, Sumio Ishikawa, Absolute stereostructure of novel chiral troponoid spiro compounds as determined by theoretical calculation of CD spectra Journal of the American Chemical Society. ,vol. 109, pp. 1661- 1665 ,(1987) , 10.1021/JA00240A010
John E. McMurry, Organic chemistry of low-valent titanium Accounts of Chemical Research. ,vol. 6, pp. 281- 286 ,(1974) , 10.1021/AR50081A001
Nobuyuki Harada, Jun Kohori, Hisashi Uda, Koji Nakanishi, Reiji Takeda, Absolute stereochemistry of (+)-1,8a-dihydro-3,8-dimethylazulene, a labile biosynthetic intermediate for 1,4-dimethylazulene. Determination by theoretical calculation of CD spectra and verification by synthesis of model compounds Journal of the American Chemical Society. ,vol. 107, pp. 423- 428 ,(1985) , 10.1021/JA00288A024
A. Moscowitz, Some applications of the kronig-kramers theorem to optical activity Tetrahedron. ,vol. 13, pp. 48- 56 ,(1961) , 10.1016/S0040-4020(01)92204-5
M. B. Groen, Hans Wynberg, Optical properties of some heterohelicenes. Absolute configuration Journal of the American Chemical Society. ,vol. 93, pp. 2968- 2974 ,(1971) , 10.1021/JA00741A025
Robert Downs Haworth, 145. Syntheses of alkylphenanthrenes. Part I. 1-, 2-, 3-, and 4-Methylphenanthrenes Journal of The Chemical Society (resumed). pp. 1125- 1133 ,(1932) , 10.1039/JR9320001125
C.M. Kemp, S.F. Mason, The absorption and circular dichroism spectra and the absolute configuration of (+)-1-fluoro-12-methylbenzo[c] phenanthrene Tetrahedron. ,vol. 22, pp. 629- 635 ,(1966) , 10.1016/0040-4020(66)80032-7
Yoshio Okamoto, Koichi Suzuki, Koji Ohta, Koichi Hatada, Heimei Yuki, Optically active poly(triphenylmethyl methacrylate) with one-handed helical conformation Journal of the American Chemical Society. ,vol. 101, pp. 4763- 4765 ,(1979) , 10.1021/JA00510A072
Motomasa Kobayashi, Nobuyoshi Shimizu, Isao Kitagawa, Yoshimasa Kyogoku, Nobuyuki Harada, Hisashi Uda, Absolute stereostructures of halenaquinol and halenaquinol sulfate, pentacyclic hydroquinones from the okinawan marine sponge xestospongia sapra, as determined by theoretical calculation of CD spectra Tetrahedron Letters. ,vol. 26, pp. 3833- 3836 ,(1985) , 10.1016/S0040-4039(00)89263-1
DAVID A. LIGHTNER, DANIEL T. HEFELFINGER, GERARD W. FRANK, THOMAS W. POWERS, KENNETH N. TRUEBLOOD, Absolute Configuration of Hexahelicene Nature. ,vol. 232, pp. 124- 125 ,(1971) , 10.1038/PHYSCI232124A0