Taniguchi Tohru, Monde Kenji, Nakanishi Koji, Berova Nina
Department of Chemistry, Columbia University, New York, NY 10027, USA.
Org Biomol Chem. 2008 Dec 7;6(23):4399-405. doi: 10.1039/b813437e. Epub 2008 Oct 16.
The optical rotation, electronic circular dichroism (ECD) and vibrational circular dichroism (VCD) of chiral sulfinates have been studied experimentally, and analysed by density functional theory calculation, aiming at establishing a reliable and convenient methodology to determine their absolute configuration. Through the study on a model chiral sulfinate with known absolute configuration, (R)-(+)-methyl p-toluenesulfinate ((R)-(+)-1), each technique was found to be reliable in assigning chirality of sulfinates. We then applied these methods to a synthetically prepared cruciferous phytoalexin, brassicanal C ((-)-2), and unambiguously determined its absolute configuration as S. The advantages and disadvantages of each spectroscopy on sulfinates are also discussed.
对手性亚磺酸盐的旋光性、电子圆二色性（ECD）和振动圆二色性（VCD）进行了实验研究，并通过密度泛函理论计算进行分析，旨在建立一种可靠且便捷的方法来确定其绝对构型。通过对具有已知绝对构型的模型手性亚磺酸盐（R）-（+）-对甲苯亚磺酸甲酯（（R）-（+）-1）的研究，发现每种技术在确定亚磺酸盐的手性方面都是可靠的。然后，我们将这些方法应用于一种合成制备的十字花科植物抗毒素——油菜素C（（-）-2），并明确确定其绝对构型为S。还讨论了每种光谱法用于亚磺酸盐时的优缺点。
