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

被引：42

作者：

Harada, N ^{[1
]}

Saito, A ^{[1
]}

Koumura, N ^{[1
]}

Uda, H ^{[1
]}

deLange, B ^{[1
]}

Jager, WF ^{[1
]}

Wynberg, H ^{[1
]}

Feringa, BL ^{[1
]}

机构：

[1] UNIV GRONINGEN,GRONINGEN CTR CATALYSIS & SYNTH,DEPT ORGAN & MOL INORGAN CHEM,NL-9747 AG GRONINGEN,NETHERLANDS

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1997年 / 119卷 / 31期

关键词：

D O I：

10.1021/ja970667u

中图分类号：

O6 [化学];

学科分类号：

0703 ;

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 chiral stationary phase, optically pure enantiomers were obtained. The CD spectra of these chiral olefins exhibit very intense Cotton effects in the B-1(b) transition region, reflecting their strongly twisted ct-electron systems. The CD and UV spectra of chiral olefins (M,M)-(E)-1 and (MM)-(Z)-2 were theoretically calculated by the pi-electron self-consistent field/configuration interaction/dipole velocity molecular orbital method. From the calculation results, the absolute stereostructures of these chiral olefins were theoretically determined to be [CD(+)239.0]-(M,M)-(E)-1 and [CD(+)238.1]-(M,M)-(2)-2, respectively.

引用

页码：7241 / 7248

页数：8

共 42 条

[21] 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 [J].