Asymmetric Hydrosilation of Aromatic Ketones Catalyzed by CuFe2O4 Nanoparticles†

doi:10.7503/cjcu20150650

Abstract

Abstract:

CuFe₂O₄ nanoparticles were synthesized by coprecipitation, sol-gel and solvothermal methods, respectively. The asymmetric hydrosilation of aromatic ketones was catalyzed by CuFe₂O₄ nanoparticles, employing (R)-BINAP[2,2'-bis(diphenylphosphino)-1,1'-binaphthalene] as chiral ligand and polymethylhydrosiloxane as hydrosilating reagent. The results showed that compared to the others, the CuFe₂O₄ nanoparticles prepared by solvothermal method had spherical shape, small size, better dispersion, uniform distribution and excellent catalytic activities. Meanwhile, it was found that the catalytic activity of the CuFe₂O₄ nanoparticles was significantly improved with the addition of t-BuOK and t-BuOH. An efficient heterogeneous catalytic system CuFe₂O₄/t-BuOK/t-BuOH was finally obtained. Under room temperature and air atmosphere, the conversion of the aromatic ketones and the enantiomeric excesses of the (R)-1-arylethanols were up to 99% and 92%, respectively, with the heterogeneous catalytic system. It was also confirmed that the electronic effect and steric hindrance of the groups on the aromatic ring distinctly affected the results of hydrosilation. And a possible mechanism was presented to explain the influence of some key factors on the reaction. Furthermore, it was demonstrated that the CuFe₂O₄ nanocatalyst could be easily separated from reaction system under an external magnetic field. And after recycling for four times, the catalyst could also have a high catalytic activity for the asymmetric hydrosilation.

Key words: Asymmetric hydrosilation, Aromatic ketone, CeFe2O4 nanoparticles, Polymethylhydrosiloxane

CLC Number:

TrendMD:

ZHU Jielian, XIA Xiaofeng, LIANG Minting, LIU Xiang, LI Hexing. Asymmetric Hydrosilation of Aromatic Ketones Catalyzed by CuFe₂O₄ Nanoparticles^†[J]. Chem. J. Chinese Universities, 2016, 37(3): 539.

Figures/Tables 9

Fig.1 SEM images of CuFe2O4 prepared by different methods(A) Coprecipitation method; (B) sol-gel method; (C) solvothermal method.

Fig.2 XRD patterns of CuFe2O4 prepared by sol-gel(a), coprecipitation(b) and solvothermal(c) methods

Table 1 Asymmetric hydrosilation of acetophenone catalyzed by CuFe2O4 nanoparticles via different methodsa

Entry	Synthetic method of CuFe₂O₄	Temperature/℃	Time/h	Conversion(%)	e.e.(%)^b
1	Coprecipitation	25	14	71	77
2	Coprecipitation	55	14	99	72
3	Sol-gel	25	14	37	75
4	Sol-gel	55	14	70	72
5	Solvothermal	25	2	99	77

Table 2 Effects of additives on the asymmetric hydrosilation of acetophenonea

Entry	n(t-BuOK)/mmol	n(t-BuOH)/mmol	Conversion(%)	e.e.^b (%)
1			66	76
2	0.03		89	77
3	0.03	3	99	77
4		3	24	75
5^c	0.03	3	<5

Table 3 Effects of substrates on the asymmetric hydrosilationa

Entry	R	Time/h	Conversion(%)	e.e.^b(%)	Entry	R	Time/h	Conversion(%)	e.e.^b(%)
1	H	2	99	77	6	4'-CH₃	2	56	77
2	2'-Cl	2	99	62	7	4'-CH₃	10	85	78
3	3'-Cl	2	99	81	8	4'-OCH₃	2	35	80
4	4'-Cl	2	99	87	9	4'-OCH₃	20	81	79
5	4'-NO₂	2	99	92

Fig.3 Magnetic separation of CuFe2O4 nanoparticles

Table 4 Recycling of CuFe2O4 nanoparticles catalyst for the asymmetric hydrosilation of acetophenonea

Entry	Times of recycling	Catalyst recovery(%)	Conversion(%)	e.e.^b(%)
1	0		99	77
2	1	89	99	77
3	2	90	94	77
4	3	89	88	76
5	4	91	80	77

Fig.4 SEM images of the original(A) and reclaimed(B) CuFe2O4 nanoparticles

Fig.5 Plausible mechanism of the asymmetric hydrosilation of aromatic ketones catalyzed by CuFe2O4 nanoparticles

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Asymmetric Hydrosilation of Aromatic Ketones Catalyzed by CuFe₂O₄ Nanoparticles^†

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