轴不对称支撑的手性N-O酰胺化合物催化亚胺硅氢化反应的过渡态研究

doi:10.7503/cjcu20140791

高等学校化学学报 ›› 2015, Vol. 36 ›› Issue (2): 325.doi: 10.7503/cjcu20140791

轴不对称支撑的手性N-O酰胺化合物催化亚胺硅氢化反应的过渡态研究

潘威¹, 马文广¹, 杨晓东¹, 郑昀晔¹, 宋碧清¹, 牛永志¹, 古吉¹, 胡栋宝², 杨芹², 朱华结²()

1. 玉溪中烟种子公司研发部, 玉溪 653100
2. 河北大学中国手性中心, 药物化学与分子诊断教育部重点实验室, 保定 071002

收稿日期:2014-09-01 出版日期:2015-02-10 发布日期:2015-01-20
作者简介:联系人简介: 朱华结, 男, 博士, 教授, 主要从事有机立体化学研究. E-mail: hjzhu@mail.kib.ac.cn
基金资助:
河北大学引进人才项目资助

Transition State Investigation on Hydrosilylation of Ketoimines with Trichlorosilane Using Asymmetric-axle-supported Chiral N-O Amides^†

PAN Wei¹, MA Wenguang^1,^*, YANG Xiaodong¹, ZHENG Junye¹, SONG Biqing¹, NIU Yongzhi¹, GU Ji¹, HU Dongbao², YANG Qin², ZHU Huajie^2,^*()

1.Yuxi Tobacco Seed Co., Ltd. Yuxi 653100, China
2. Chinese Centre for Chirality, Key Laboratory of Medicinal Chemistry and Molecular College of Pharmacy of Sciences of Hebei University, Baoding 071002, China

Received:2014-09-01 Online:2015-02-10 Published:2015-01-20
Contact: MA Wenguang,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：

利用Hartree-Fock(HF)算法和密度泛函理论(DFT)探讨了新型轴手性氮氧酰胺类配体催化亚胺C=N双键不对称硅氢化反应的过渡态. 研究发现, H在Si原子上, 反应经过渡态TS-2, 能垒较低, 由此得到产物(-)-N-(1-phenylethyl)aniline的e.e.值与实验结果相吻合. 同时, 本文还尝试采用合理的简化模型计算反应过渡态, 其结果与使用全部分子用于过渡态能量计算的结论一致.

关键词: 硅氢化反应, 过渡态, 密度泛函理论, 绝对构型, 手性氮氧酰胺化合物

Abstract:

The mechanism was investigated for enantioselective hydrosilylation of C=N with HSiCl₃ catalyzed by a novel asymmetric-axle-supported chiral ligand with Hartree-Fock(HF) and density functional theory(DFT) at the 6-31G(d) basis sets, respectively. Molecules of catalyst, ketoimine and HSiCl₃ were included in activation energy computations. The energy barriers can well explain the enantioselective reaction e.e. values recorded in experiments. Also, a simplified transition state(TS) model was adopted in TS calculations, the barrier sequence recorded by the model had a good agreement with the results via using whole substances[catalyst 3 or epi-3, SiHCl₃ and (-)-N-(1-phenylethylidene)aniline] in TS calculations, including the e.e. values.

Key words: Hydrosilylation, Transition state, Density functional theory, Absolute configuration, Chiral N-O amide

中图分类号:

O641

TrendMD:

潘威, 马文广, 杨晓东, 郑昀晔, 宋碧清, 牛永志, 古吉, 胡栋宝, 杨芹, 朱华结. 轴不对称支撑的手性N-O酰胺化合物催化亚胺硅氢化反应的过渡态研究. 高等学校化学学报, 2015, 36(2): 325.

PAN Wei, MA Wenguang, YANG Xiaodong, ZHENG Junye, SONG Biqing, NIU Yongzhi, GU Ji, HU Dongbao, YANG Qin, ZHU Huajie. Transition State Investigation on Hydrosilylation of Ketoimines with Trichlorosilane Using Asymmetric-axle-supported Chiral N-O Amides^†. Chem. J. Chinese Universities, 2015, 36(2): 325.

图/表 8

Fig.1 Hydrosilylation of ketoimines with trichlorosilane using asymmetric-axle-supported chiral N-O amides(3)

Fig.2 Catalyst 3, epi-3 and the proposed TS structures

Fig.3 Three possible TS types involved in the hydrosilylations

Table 1 Relative TS barriers found in types A to C and the AC of hydrosilylation product N-(1-phenylethyl)aniline

Type	ΔE/(kJ·mol^-1)	ΔE₀/(kJ·mol^-1)	ΔG/(kJ·mol^-1)	Chiral
A(TS-1)	15.09	18.22	20.26	R
A(TS-3)	1.22	3.98	3.68	R
A(TS-4)	4.30	5.19	0	S
A(TS-2)	0	0	1.56	S
B	104.06	103.09	94.58	R
B	79.61	$— b$		R
B	80.22	80.04	73.09	S
C	97.59	97.81	87.55	R
C	69.95	69.60	68.99	R
C	81.12			S

Table 1 Relative TS barriers found in types A to C and the AC of hydrosilylation product N-(1-phenylethyl)aniline

Type	ΔE/(kJ·mol^-1)	ΔE₀/(kJ·mol^-1)	ΔG/(kJ·mol^-1)	Chiral
A(TS-1)	15.09	18.22	20.26	R
A(TS-3)	1.22	3.98	3.68	R
A(TS-4)	4.30	5.19	0	S
A(TS-2)	0	0	1.56	S
B	104.06	103.09	94.58	R
B	79.61	$— b$		R
B	80.22	80.04	73.09	S
C	97.59	97.81	87.55	R
C	69.95	69.60	68.99	R
C	81.12			S

Fig.4 3D TS structures with barriers

Table 2 Predicted relative barriers

TS-x	ΔE/(kJ·mol^-1)	ΔE₀/(kJ·mol^-1)	ΔG/(kJ·mol^-1)
TS-1	11.25	13.75	14.88
TS-2	0	0	0
TS-3	5.29	5.29	4.33
TS-4	2.34	3.19	0.84

Fig.5 Simplified TS model

Table 3 Relative barriers and predicted e.e. values for (-)-2a and it’s chiral[TS-1 and TS-3 lead to 2a with(R), TS-2 and TS-4 lead to 2a with (S)]

Species	ΔE/(kJ·mol^-1)			ΔE₀/(kJ·mol^-1)			ΔG/(kJ·mol^-1)
Species	Model	DFT^a	HF^b	Model	DFT	HF	Model	DFT	HF
TS-1	17.19	11.25	15.09	19.82	13.75	18.22	20.36	14.88	20.24
TS-2	0	0	0	0	0	0	0	0	1.56
TS-3	4.43	2.73	1.22	5.54	5.29	3.98	4.48	4.33	3.68
TS-4	9.97	2.34	4.30	8.83	3.19	5.19	4.68	0.84	0
Chiral	S	S	S	S	S	S	S	S	S
e.e.(%)^c	76	16	34	80	82	70	75	81	76
e.e.(%)^d	95	80	84	98	97	88	96	97	95

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轴不对称支撑的手性N-O酰胺化合物催化亚胺硅氢化反应的过渡态研究

Transition State Investigation on Hydrosilylation of Ketoimines with Trichlorosilane Using Asymmetric-axle-supported Chiral N-O Amides^†

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轴不对称支撑的手性N-O酰胺化合物催化亚胺硅氢化反应的过渡态研究

Transition State Investigation on Hydrosilylation of Ketoimines with Trichlorosilane Using Asymmetric-axle-supported Chiral N-O Amides†

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Transition State Investigation on Hydrosilylation of Ketoimines with Trichlorosilane Using Asymmetric-axle-supported Chiral N-O Amides^†