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

doi:10.7503/cjcu20140791

Abstract

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

CLC Number:

O641

TrendMD:

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^†[J]. Chem. J. Chinese Universities, 2015, 36(2): 325.

Figures/Tables 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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