Conformational Equilibria of TADDOL-s in Solution Investigated by Vibrational Circular Dichroism

被引：7

作者：

Uncuta, Cornelia ^{[2
]}

Bartha, Emeric ^{[2
]}

Gherase, Dragos ^{[2
]}

Teodorescu, Florina ^{[2
]}

Draghici, Constantin ^{[2
]}

Cavagnat, Dominique ^{[1
]}

Daugey, Nicolas ^{[1
]}

Liotard, Daniel ^{[1
]}

Buffeteau, Thierry ^{[1
]}

机构：

[1] Univ Bordeaux 1, CNRS, UMR5255, Inst Mol Sci, F-33405 Talence, France

[2] Acad Romana, Ctr Organ Chem Costin D Nenitescu, Bucharest 060023, Romania

来源：

CHIRALITY | 2010年 / 22卷 / 1E期

关键词：

vibrational circular dichroism; DFT calculations; conformational analysis; TADDOL; CHIRAL MOLECULES; DERIVATIVES; AUXILIARIES; COMPLEXES;

D O I：

10.1002/chir.20829

中图分类号：

R914 [药物化学];

学科分类号：

100701 ;

摘要：

Six enantiomeric pairs of TADDOL-s gathered in two series with either methyl (series A) or phenyl (series B) substituent in 2-position of the dioxolane ring were studied by vibrational circular dichroism (VCD). Experimental IR and VCD spectra associated with density functional theory (DFT) calculations showed that the two series exhibit quite different conformations in solution. In series A, the conformer with anti C-O bonds and stabilized by intramolecular OH ... OH hydrogen bonding prevails, whereas in series B the conformer with gauche C-O bonds and intramolecular OH ... pi hydrogen bonding is favored. The shape and sign of the VCD bands in the O-H stretching region revealing the nature of the intramolecular hydrogen bonding were clearly identified. Polarimetric measurements showed that, within the same absolute configuration, compounds in series A and in series B have opposite signs of optical rotation. Chirality 22:E115-E122, 2010. (c) 2010 Wiley-Liss, Inc.

引用

页码：E115 / E122

页数：8

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