Absolute configuration determination of donor-acceptor [2.2]paracyclophanes by comparison of theoretical and experimental vibrational circular dichroism spectra

被引：15

作者：

Furo, T

Mori, T

Origane, Y

Wada, T

Izumi, H

Inoue, Y

机构：

[1] Osaka Univ, Dept Mol Chem, Grad Sch Engn, Suita, Osaka 5650871, Japan

[2] JST, ICORP, Entropy Control Project, Toyonaka, Osaka, Japan

[3] AIST Tuskuba W, Natl Inst Adv Ind Sci & Technol, Ibaraki, Japan

来源：

CHIRALITY | 2006年 / 18卷 / 03期

关键词：

vibrational circular dichroism spectroscopy; DFT calculation; charge-transfer interaction; exciton coupling method; chiral cyclophane;

D O I：

10.1002/chir.20233

中图分类号：

R914 [药物化学];

学科分类号：

100701 ;

摘要：

Vibrational circular dichroism (VCD) spectra were obtained for the assignments of the absolute configurations of diastereomeric 4,7-bis(methoxycarbonyl)12,15-dimethoxy-[2.2]paracyclophanes (1 and 2), and density functional theory (DFT) calculations were performed at the B3LYP/6-31G(d) level for all possible conformations of both 1 and 2 to give the theoretical VCD spectra. Comparisons of the experimental and theoretical VCD spectra obtained unambiguously established the absolute configurations of the dextrorotatory (+)-enantiomers as (4S(p);12S(p))-1 and (4S(p));12R(p))-2, respectively.) (c) 2006 Wiley-Liss, Inc.

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页码：205 / 211

页数：7

相关论文

共 30 条

[1] Conformations of chiral molecules in solution:: Ab initio vibrational absorption and circular dichroism studies of 4,4a,5,6,7,8-hexahydro-4a-methyl-2(3H)-naphthalenone and 3,4,8,8a-tetrahydro-8a-methyl-1,6(2H,7H)-naphthalenedione [J].

Aamouche, A ;

Devlin, FJ ;

Stephens, PJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (30) :7358-7367

[2] Structure, vibrational absorption and circular dichroism spectra, and absolute configuration of Troger's Base [J].

Aamouche, A ;

Devlin, FJ ;

Stephens, PJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (10) :2346-2354

[3] Theoretical UV circular dichroism of aliphatic cyclic dipeptides [J].

Carlson, KL ;

Lowe, SL ;

Hoffmann, MR ;

Thomasson, KA .

JOURNAL OF PHYSICAL CHEMISTRY A, 2005, 109 (24) :5463-5470

[4] Prediction of vibrational circular dichroism spectra using density functional theory: Camphor and fenchone [J].

Devlin, FJ ;

Stephens, PJ ;

Cheeseman, JR ;

Frisch, MJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (26) :6327-6328

[5] Absolute configuration determination of chiral molecules in the solution state using vibrational circular dichroism [J].

Freedman, TB ;

Cao, XL ;

Dukor, RK ;

Nafie, LA .

CHIRALITY, 2003, 15 (09) :743-758

[6] Determination of absolute configuration in molecules with chiral axes by vibrational circular dichroism:: A C2-symmetric annelated heptathiophene and a D2-symmetric dimer of 1,1′-binaphthyl [J].

Freedman, TB ;

Cao, XL ;

Rajca, A ;

Wang, H ;

Nafie, LA .

JOURNAL OF PHYSICAL CHEMISTRY A, 2003, 107 (39) :7692-7696

[7]

FRISCH MJ, 1998, GAUSSIAN 98 REV A 11

[8] Absolute configuration of chiral [2.2]paracyclophanes with intramolecular charge-transfer interaction. Failure of the exciton chirality method and use of the sector rule applied to the cotton effect of the C-T transition (vol 127, pg 8242, 2005) [J].

Furo, T ;

Mori, T ;

Wada, T ;

Inoue, Y .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (46) :16338-16338

[9] Absolute configuration of chiral [2.2]paracyclophanes with intramolecular charge-transfer interaction. Failure of the exciton chirality method and use of the sector rule applied to the cotton effect of the CT transition [J].

Furo, T ;

Mori, T ;

Wada, T ;

Inoue, Y .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (23) :8242-8243

[10] [2.2]Paracyclophane derivatives in asymmetric catalysis [J].

Gibson, SE ;

Knight, JD .

ORGANIC & BIOMOLECULAR CHEMISTRY, 2003, 1 (08) :1256-1269