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

doi:10.7503/cjcu20131023

Abstract

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)

CLC Number:

O629.9

TrendMD:

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^†[J]. Chem. J. Chinese Universities, 2014, 35(4): 746.

Figures/Tables 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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