从草酸青霉菌中分离得到的立体异构体Hydroxyscytalone的光谱学研究

doi:10.7503/cjcu20131023

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (4): 746.doi: 10.7503/cjcu20131023

从草酸青霉菌中分离得到的立体异构体Hydroxyscytalone的光谱学研究

纪彦南, 何平, 李金亮, 郭秀杰, 王香粉, 俞和, 申世刚, 朱华结()

河北大学中国手性中心, 化学与环境科学学院, 药物化学与分子诊断教育部重点实验室, 保定 071002

收稿日期:2013-10-21 出版日期:2014-04-10 发布日期:2014-03-14
作者简介:联系人简介: 朱华结, 男, 博士, 教授, 主要从事手性天然产物的发现以及手性催化剂设计合成在手性药物设计中的应用. E-mail: hjzhu@mail.kib.ac.cn
基金资助:
河北大学人才引进项目资助

Stereochemistry of Hydroxyscytalone Isolated from Penicillium Oxalicum Using VCD, ECD and OR Methods^†

JI Yannan, HE Ping, LI Jinliang, GUO Xiujie, WANG Xiangfen, YU He, SHEN Shigang, ZHU Huajie^*()

Chinese Center for Chirality, College of Chemistry and Environmental Science, Key Laboratory of Medicinal Chemistry and Molecular Diagnostics, Ministry of Education, Hebei University, Baoding 071002, China

Received:2013-10-21 Online:2014-04-10 Published:2014-03-14
Contact: ZHU Huajie E-mail:hjzhu@mail.kib.ac.cn
Supported by:
† Supported by the Talents Program of Hebei University, China.

摘要/Abstract

摘要：

从真菌草酸青霉菌(Penicillium oxalicum)中分离得到一个新的立体异构体Hydroxyscytalone, 其平面结构采用核磁共振和高分辨质谱等进行确定, 其立体化学通过振动圆二色光谱、电子圆二色光谱和旋光光谱进行证实.

关键词: Hydroxyscytalone, 草酸青霉菌, 振动圆二色光谱, 电子圆二色光谱, 旋光

Abstract:

A new stereoisomer of hydroxyscytalone from Penicillium oxalicum was obtained. Its planar structure was established using ¹H NMR, ¹³C NMR and high resolution MS. In its stereochemistry study, the very recently developed method, vibrational circular dichroism(VCD) was used. The calculation is relatively simple by computing the corresponding characteristics based on ground state of electronics. By comparison of computed VCD, ECD and OR with the experimental data, stereochemistry can be well studied.

Key words: Hydroxyscytalone, Penicillium oxalicum, Vibrational circular dichroism(VCD), Electronic circular dichroism(ECD), Optical rotation(OR)

中图分类号:

O629.9

TrendMD:

纪彦南, 何平, 李金亮, 郭秀杰, 王香粉, 俞和, 申世刚, 朱华结. 从草酸青霉菌中分离得到的立体异构体Hydroxyscytalone的光谱学研究. 高等学校化学学报, 2014, 35(4): 746.

JI Yannan, HE Ping, LI Jinliang, GUO Xiujie, WANG Xiangfen, YU He, SHEN Shigang, ZHU Huajie. Stereochemistry of Hydroxyscytalone Isolated from Penicillium Oxalicum Using VCD, ECD and OR Methods^†. Chem. J. Chinese Universities, 2014, 35(4): 746.

图/表 5

Fig.1 Structures of compound 1 and its four isomers

Table 1 Reported different stereo structures of compound 1 and its corresponding optical properties

Structure	Config.	CD		OR	Structure	Config.	CD		OR
Structure	Config.	λ/nm	[θ]		Structure	[α $] D t$	λ/nm	[θ]	[α $] D t$
	cis-	237^[14]	-3737	-56°^[15]		(3S,4S)			+57.9°^[21]
		279	-6684
		305	+3579
	trans-	239^[14]	-4545
		279	-9441			(3S,4R)	218^[22]	+20460	-62.37°^[23]
		305	-629				233	-8580
		317	-1119				268	-7920
		329	-699				302	+4950
				-75°^[20]

Table 1 Reported different stereo structures of compound 1 and its corresponding optical properties

Structure	Config.	CD		OR	Structure	Config.	CD		OR
Structure	Config.	λ/nm	[θ]		Structure	[α $] D t$	λ/nm	[θ]	[α $] D t$
	cis-	237^[14]	-3737	-56°^[15]		(3S,4S)			+57.9°^[21]
		279	-6684
		305	+3579
	trans-	239^[14]	-4545
		279	-9441			(3S,4R)	218^[22]	+20460	-62.37°^[23]
		305	-629				233	-8580
		317	-1119				268	-7920
		329	-699				302	+4950
				-75°^[20]

Fig.2 Comparison of the experimental VCDs and IRs to the computed VCDs and IRs for (3R,4R)-1 and (3S,4R)-1(A, A') Computed and experimental VCDs of (3R,4R)-1, respectively; (B, B') computed and experimental IRs of (3R,4R)-1, respectively; (C, C') computed and experimental VCDs of (3S,4R)-1, respectively; (D, D') computed and experimental IRs of (3S,4R)-1, respectively.

Fig.3 Comparison of predicted VCDs with the experimental VCDs for (3S,4S)-1 and (3R,4S)-1 (A, A') Predicted and experimental VCDs for (3S,4S)-1, respectively; (B, B') Predicted and experimental VCDs for (3R,4S)-1, respectively.

Fig.4 Comparison of the predicted ECD(a) for (3R,4R)-1(A) and (3S,4R)-1(B) to the experimental ECD(b) for(-)-1

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从草酸青霉菌中分离得到的立体异构体Hydroxyscytalone的光谱学研究

Stereochemistry of Hydroxyscytalone Isolated from Penicillium Oxalicum Using VCD, ECD and OR Methods^†

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从草酸青霉菌中分离得到的立体异构体Hydroxyscytalone的光谱学研究

Stereochemistry of Hydroxyscytalone Isolated from Penicillium Oxalicum Using VCD, ECD and OR Methods†

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Stereochemistry of Hydroxyscytalone Isolated from Penicillium Oxalicum Using VCD, ECD and OR Methods^†