Absolute configurations of endoperoxides determined by vibrational circular dichroism (VCD)
Absolute configurations of endoperoxides determined by vibrational circular dichroism (VCD)
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DOI：
10.1016/j.tetlet.2006.04.089
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发表时间：
2006-06-26
影响因子：
1.8
通讯作者：
Suzuki, Minoru
中科院分区：
文献类型：
--
作者：
Monde, Kenji;Taniguchi, Tohru;Suzuki, Minoru
通过HPLC在手性柱上有效地分离了所有内过氧化物乙酰基majapolene A（1）的过氧化物部分上的非对映异构体混合物，并进行了振动圆二色性（VCD）研究。采用密度泛函理论（DFT）方法，在B3 PW 91/6- 31 G（d.p）水平上对1a和1b进行了从头算VCD和IR计算.通过对过氧化物振动带的研究，确定了1a和1b的绝对构型分别为（1 R，4 R，7S，10 S）和（1 S，4S，7S，10 S）。这是第一次将VCD应用于自然界中大量存在的内过氧化物。(c)2006爱思唯尔有限公司保留所有权利。
Diastercomeric mixture on the peroxide portion of ail endoperoxide acetylmajapolene A (1) was efficiently separated by HPLC on a chiral column, submitting to vibrational circular dichroism (VCD) investigation. The ab initio theoretical VCD and IR calculations of 1a and 1b were performed by density functional theory (DFT) using the B3PW91/6-31G(d.p) level of theory. Focusing on an isolated characteristic peroxide vibrational band, absolute configurations of 1a and 1b were unambiguously determined Lis (1R,4R,7S,10S) and (1S,4S,7S,10S), respectively. This is the first VCD application to endoperoxides which exist abundantly in nature. (c) 2006 Elsevier Ltd. All rights reserved.