Nuclear Magnetic Resonance Assignment and Crystal Structure of 3, 22-Dihydroxyhopane

doi:10.11938/cjmr20202840

Abstract

Abstract:

Pure α- and β- isomers of 3, 22-dihydroxyhopane were obtained by the reduction of hydroxyl protected hydroxyhopanone with L-selectride. The absolute configuration of 3β, 22-hydroxyhopane was confirmed by single crystal X-ray diffraction, and the unambiguous ¹H and ¹³C NMR data of two isomers were fully assigned for the first time. The preparation method is suitable for the separation of other unseparated α, β-isomers.

Key words: 3, 22-dihydroxyhopane, ¹H NMR, ¹³C NMR, absolute configuration

CLC Number:

Lei JIANG,Yang FU,Wen-wen GUO,Guo ZHENG,Qiang WANG. Nuclear Magnetic Resonance Assignment and Crystal Structure of 3, 22-Dihydroxyhopane[J]. Chinese Journal of Magnetic Resonance, 2021, 38(2): 255-267.

Figures/Tables 10

Fig.1

Fig.2

Fig.3

Table 1

Fig.4

Fig.5

Table 2

Fig.6

Fig.7

Table 3

1H and 13C NMR experimental data (Solvent: Pyridine-d5) and documentary data (Solvent: CDCl3) of compounds 1

No.	实验					文献^[2] CDCl₃
No.	δ_H (J/Hz)	δ_C	HMBC	¹H-¹H COSY	NOESY	δ_H (J/Hz)	δ_C
1a	1.78 (1H, m)	34.3（仲）					33.2
1b	1.49 (1H, m)
2a	2.05 (1H, m)	27.0（仲）	C-10	H-2b, 3	H-25		25.3
2b	1.81 (1H, m)			H-2a, 3
3	3.65 (1H, t, 2.8)	75.7（叔）	C-1, 5, 24	H-2	H-23, 24	3.39 (1H, t, 3.1)	76.2
4	/	38.5（季）					37.5
5	1.66 (1H, dd, 11.9/1.5)	49.5（叔）	C-4, 6, 7, 9, 10, 23, 24, 25		H-23		48.8
6a	1.51 (1H, m)	19.1（仲）					18.3
6b	1.43 (1H, m)
7a	1.53 (1H, m)	34.1（仲）					33.2
7b	1.21 (1H, m)
8	/	42.558（季）					41.8
9	1.47 (1H, m)	50.9（叔）					50.0
10	/	38.0（季）					37.2
11a	1.62 (1H, m)	21.7（仲）					20.9
11b	1.35 (1H, m)
12	1.44 (2H, m)	24.9（仲）					24.1
13	1.44 (1H, m)	50.6（叔）					49.9
14	/	42.575（季）					41.9
15a	1.40 (1H, m)	35.1（仲）					34.7
15b	1.23 (1H, m)
16a	2.21(1H, ddt, 12.9/4.5/2.4)	22.7（仲）	C-14, 15, 18	H-15, 16b	H-29, 30		21.9
16b	1.80 (1H, m)			H-15, 16a
17	1.53 (1H, m)	55.1（叔）					53.9
18	/	44.8（季）					44.1
19a	1.60 (1H, m)	42.2（仲）					41.3
19b	1.00 (1H, m)
20a	1.83 (1H, m)	27.4（仲）					26.6
20b	1.78 (1H, m)
21	2.40 (1H, dt, 11.1/8.9)	52.0（叔）	C-17, 18, 20, 22, 29, 30	H-17, 20	H-29, 30		51.1
22	/	72.7（季）					73.9
23	1.25 (3H, s)	29.8（伯）	C-3, 4, 5, 24		H-3, 5	0.76	28.3
24	0.94 (3H, s)	23.0（伯）	C-3, 4, 5, 23		H-3	0.94	22.1
25	0.93 (3H, s)	16.5（伯）	C-1, 5, 9, 10		H-2a	0.83	15.7
26	1.03 (3H, s)	17.4（伯）	C-7, 8, 9, 14			0.96	17.0
27	0.90 (3H, s)	17.6（伯）	C-8, 13, 14, 15			0.96	17.1
28	0.93 (3H, s)	16.9（伯）	C-13, 17, 18, 19			0.76	16.2
29	1.38 (3H, s)	30.3（伯）	C-21, 22, 30		H-16a, 21	1.18	28.7
30	1.43 (3H, s)	31.9（伯）	C-21, 22, 29		H-16a, 21	1.21	30.9
3-OH	/	/
22-OH	/	/

Table 3

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分子式（Formula）	C₃₀H₅₂O₂
分子量（Formula weight）	444.73
温度（Temperature）	293(2) K
λ (Cu K)	1.54178 Å
晶系（Crystal system）	单斜晶系（Monoclinic）
空间群（Space group）	C2
晶胞参数（Unit cell dimensions）	a=32.6725(12) Å, α=90° b=7.3866(2) Å, β=96.463(3)° c=11.0375(3) Å, γ=90°
体积（Volume）	2646.85(14) Å³
晶胞中最小不对称单元个数Z	4
计算密度（Calculated Density）	1.166 g·cm^-³
Reflections collected /unique	6531/4142
吸收系数（Absorption coefficient）	0.551 mm^-¹
F(000)	1036
θ	4.03° ~76.40°
拟合优度（GOF）	1.075
最终R指数（I > 2sigma(I)）^*	R₁=0.0769, wR₂=0.2114

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