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

doi:10.7503/cjcu20160228

Abstract

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

CLC Number:

O629.9

TrendMD:

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[J]. Chem. J. Chinese Universities, 2016, 37(11): 1993.

Figures/Tables 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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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

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