天然产物的绝对构型研究(Ⅱ)——通过比较旋光和碳氢谱的实验值与计算值确定生物碱类化合物的绝对构型

doi:10.7503/cjcu20160228

摘要/Abstract

摘要：

在研究天然产物绝对构型的过程中, 筛选了一些绝对构型未确定的生物碱类化合物, 利用密度泛函理论(DFT)在不同的计算水平下得出其旋光和碳氢谱数据. 理论值与实测值对比分析结果表明, 二者基本符合, 从而鉴定出这些化合物的绝对构型.

关键词: 天然产物, 生物碱, 密度泛函理论(DFT), 旋光, 绝对构型

Abstract:

In order to study the absolute configuration of natural product, some compounds of undetermined absolute configuration were screened, the optical rotation(OR), ¹³C NMR and ¹H NMR data were gotten by density functional theory(DFT) at different computational levels. The computational results matched the experimental results well. The results show that the PCM solvent model could improve the accuracy of computed optical rotation for the rigid alkaloid molecules but not be applicable to flexible ones. Therefore, the chira-lity centers of these alkaloids were determined.

Key words: Natural product, Alkaloid, Density functional theory, Optical rotation, Absolute configuration

中图分类号:

O629.9

TrendMD:

胡栋宝, 周北斗. 天然产物的绝对构型研究(Ⅱ)——通过比较旋光和碳氢谱的实验值与计算值确定生物碱类化合物的绝对构型. 高等学校化学学报, 2016, 37(11): 1993.

HU Dongbao, ZHOU Beidou. Absolute Configuration Determination for Natural Products(Ⅱ)^†-Absolute Configuration Determination for Alkaloids by Comparing Computed Optical Rotations, ¹³C NMR and ¹H NMR with the Experimental Results. Chem. J. Chinese Universities, 2016, 37(11): 1993.

图/表 4

Fig.1 Structures of compounds 1—7

Fig.2 Optimized structures and the most stable conformers of compounds 1—7

Table 1 Calculated, experimental optical rotations(ORs) for compounds 1—7 at the different levels

Config.^a	No.^b	[α]_{D, expt}/(°)	[α]_{D, calcd}/(°)	[α $] D, sp c$ /(°)
(6aS,7S)-1	1	-102.7	-156.73^d, -153.51^e	-96.72^f, -94.98^g
(6aS,7R)-2	1	-121.5	-235.89^d, -231.08^e	-188.5^f, -183.46^g
(5bS)-3	2	-90	-135^e	-94.4^g
(8S,14R)-4	2	+198	+152.5^e	+98.6^g
(2'S)-5	4	+52	+48.2^h	+20.4ⁱ
(3S)-6	3	-144.2	-88.5^h	-80ⁱ
(4S, 5S)-7	8	-12	-49.6^d, -43.04^j, -50.32^k	-92.46^f, -84.09^l, -93.79^m

Table 1 Calculated, experimental optical rotations(ORs) for compounds 1—7 at the different levels

Config.^a	No.^b	[α]_{D, expt}/(°)	[α]_{D, calcd}/(°)	[α $] D, sp c$ /(°)
(6aS,7S)-1	1	-102.7	-156.73^d, -153.51^e	-96.72^f, -94.98^g
(6aS,7R)-2	1	-121.5	-235.89^d, -231.08^e	-188.5^f, -183.46^g
(5bS)-3	2	-90	-135^e	-94.4^g
(8S,14R)-4	2	+198	+152.5^e	+98.6^g
(2'S)-5	4	+52	+48.2^h	+20.4ⁱ
(3S)-6	3	-144.2	-88.5^h	-80ⁱ
(4S, 5S)-7	8	-12	-49.6^d, -43.04^j, -50.32^k	-92.46^f, -84.09^l, -93.79^m

Fig.3 Real configuration of compounds 1—7

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