Development of efficient solid chiral catalysts with designable linkage for asymmetric transfer hydrogenation of quinoline derivatives

doi:10.1016/S1872-2067(20)63764-0

Abstract

Abstract:

Developing chiral solid catalysts for asymmetric catalysis is desirable for the elimination of homogeneous catalysis flaws but remains an immense challenge. Herein, we report the immobilization of TsDPEN on SBA-15 with an ionic liquid (IL) linkage via the one-pot reaction of imidazole-TsDPEN-N-Boc with 3-(trimethoxysilyl)propyl bromide in the SBA-15 mesopores. After coordination to Rh, the chiral solid catalysts could efficiently catalyze quinoline transfer hydrogenation, achieving 97% conversion with 93% ee, which was comparable to their homogeneous counterparts. The chiral solid catalyst with the IL linkage afforded much higher turnover frequency than that without the IL linkage (93 h^-1 vs. 33 h^-1), attributed to the phase transfer and formate-enriching ability of the IL linkage. Furthermore, the effect of the pH on the reaction rate of the solid catalyst was investigated, preventing reaction rate retardation during the catalytic process. The tuning of the linkage group is an efficient approach for catalytic activity improvement of immobilized chiral catalysts.

Key words: Heterogeneous asymmetric catalysis, Asymmetric transfer hydrogenation, Quinolines, Imidazolate, Ionic liquid, N-(p-toluenesulfonyl)-1, 2-diphenylethylenediamine

Yiqi Ren, Lin Tao, Chunzhi Li, Sanjeevi Jayakumar, He Li, Qihua Yang. Development of efficient solid chiral catalysts with designable linkage for asymmetric transfer hydrogenation of quinoline derivatives[J]. Chinese Journal of Catalysis, 2021, 42(9): 1576-1585.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(20)63764-0

https://www.cjcatal.com/EN/Y2021/V42/I9/1576

Figures/Tables 9

Fig. 1. FT-IR spectra of imidazole-TsDPEN-N-Boc (a) and SBA-ILBF4-TsDPEN50 (b); (c) 13C NMR spectrum of imidazole-TsDPEN-N-Boc in CDCl3; (d) 13C CP/TOSS NMR spectrum of SBA-ILBF4-TsDPEN50.

Table 1 Physicochemical parameters of SBA-15, SBA-ILBF4-TsDPENx and SBA-TsDPEN25 before and after coordination with the Rh complex a.

Sample	S_BET (m²/g)	D_p (nm)	V_p (cm³/g)	S content^b (mmol/g)	C content ^b (mmol/g)	Rh content^c (mmol/g)	Weight loss ^d (wt%)	(CH₂)₃Br ^e (wt%)
SBA-15	713	7.5	0.82	—	—	—	—	—
SBA-ILBF₄-TsDPEN₂₀	407 (372)	6.4 (6.4)	0.64 (0.54)	0.16	6.9	(0.09)	17.4	8.4
SBA-ILBF₄-TsDPEN₃₅	315 (250)	6.3 (5.4)	0.46 (0.37)	0.35	12.2	(0.21)	24.7	5.7
SBA-ILBF₄-TsDPEN₅₀	311 (252)	5.4 (5.4)	0.46 (0.38)	0.39	12.7	(0.23)	27.3	5.9
SBA-TsDPEN₂₅	341 (256)	5.4 (5.5)	0.47 (0.36)	0.65	14.4	(0.20)	25.1	—

Fig. 2. (a) TGA curves; (b) N2 sorption isotherms (inset is the pore size distribution curves); (c) XRD patterns; (d) TEM image of SBA-ILBF4-TsDPEN50.

Table 2 Quinaldine asymmetric transfer hydrogenation over homogeneous or heterogeneous catalysts a.

Entry	Catalyst	T (h)	Conv. (%)	ee (%)	TOF (h^-1) ^b
1	Cp^*Rh-TsDPEN	12	95	95	75
2	SBA-ILBF₄-TsDPEN₂₀-Rh	12	86	91	92
3	SBA-ILBF₄-TsDPEN₃₅-Rh	12	86	91	63
4	SBA-ILBF₄-TsDPEN₅₀-Rh	12	84	91	63
5	SBA-ILBF₄-TsDPEN₅₀-Rh	2	62	93	—
6	SBA-ILBF₄-TsDPEN₅₀-Rh ^c	2	62	93	—
7	SBA-ILBF₄-TsDPEN₅₀-Rh ^d	1	38	—	—
8	SBA-ILBF₄-TsDPEN₅₀-Rh ^e	12	93	92	—
9	SBA-ILBF₄-TsDPEN₅₀-Rh ^f	12	96	93	93
10	SBA-TsDPEN₂₅-Rh ^f	12	90	92	33
11	SBA-TsDPEN₂₀-ILBF₄-Rh ^f	12	90	93	60

Fig. 3. (a) Reaction profiles as a function of reaction time of SBA-ILBF4-TsDPENx-Rh and TsDPEN-Rh in quinaldine ATH (5 μmol Rh, 0.5 mmol quinaldine, 5 mmol HCOONa·2H2O and 5.0 mL of 2 M HOAc-NaOAc buffer with an initial pH of 5, 40 °C). (b) Reaction rate and enantioselectivity of quinaldine ATH with different S/C ratios over SBA-ILBF4-TsDPEN50-Rh (5 mmol HCOONa·2H2O, 5.0 mL of 2 M HOAc-NaOAc buffer with an initial pH of 5, 40 °C, 20 min).

Fig. 4. (a) Reaction solution pH with respect to time during quinaldine ATH catalyzed by SBA-ILBF4-TsDPEN50-Rh or SBA-TsDPEN25-Rh (5 μmol Rh, 0.5 mmol quinaldine, 5 mmol HCOONa·2H2O, and 5.0 mL of 2 M/4 M buffer with pH = 5, 40 °C). (b) Reaction profiles as a function of time for SBA-ILBF4-TsDPEN50-Rh and SBA-TsDPEN25-Rh in quinaldine ATH (5 μmol Rh, 0.5 mmol quinaldine, 5 mmol HCOONa·2H2O, and 5.0 mL of 4 M HOAc-NaOAc buffer with an initial pH of 5, 40 °C) and hot filtration test for the ATH reaction with SBA-ILBF4-TsDPEN50-Rh (red dot = after filtering SBA-ILBF4-TsDPEN50-Rh).

Table 3 Asymmetric transfer hydrogenation of substituted quinoline derivatives with SBA-ILBF4-TsDPEN50-Rh a.


Entry	R¹	R²	Conversion ^b (%)	ee ^c (%)
1	Me	Me	87	94
2 ^d	H	Et	89	90
3 ^d	H	n-Pr	87	90
4 ^d	H	n-Bu	88	90
5 ^d	H	n-Pentyl	79	89
6	F	Me	80	90
7 ^e	Br	Me	83	90

Fig. 5. Recyclability of SBA-ILBF4-TsDPEN50-Rh in the asymmetric transfer hydrogenation of quinaldine (the reaction times for cycles 1, 2, 3, 4, and 5 are 2, 2, 3, 6, and 12 h, respectively).

Fig. 6. Scheme 1. SBA-ILBF4-TsDPENx-Rh synthesis and chiral ligand immobilization on SBA-15 via alkane linkage (SBA-TsDPEN25-Rh).

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