C2-Symmetric Bisprolinamide Chiral Polymer Catalyst with Double Decker Silsesquioxane in Main Chain for the Asymmetric Aldol Reactions†

doi:10.7503/cjcu20170298

Abstract

Abstract:

Double-decker silsesquioxane(DDSQ) and tert-butyl oxygen carbonyl(Boc) protection of C₂-symmetric bisprolinamide were used to prepare C₂-symmetric bisprolinamide chiral polymer catalyst with DDSQ in the main chain. The chiral polymer catalyst was prepared by silicon hydrogen addition reaction and Boc deprotection. The structure of the prepared polymer catalyst was characterized by means of ¹H NMR, ¹³C NMR and ²⁹Si NMR. The molecular weight and thermal property of the prepared polymer catalyst were characterized by means of GPC and TGA. The polymer catalyst was applied in asymmetric Aldol reaction to study the catalytic function, and the products were obtained in good yields and stereoselectivities. Moreover, the polymer catalyst could be readily recovered and recycled for further transformations at least six cycles without observing significant decrease in yield and stereoselectivity.

Key words: Double-decker silsesquioxane, C₂-Symmetric bisprolinamide, Chiral catalyst, Aldol reaction

CLC Number:

O621.3

TrendMD:

SHEN Jinrui, ZHOU Zhe, ZHOU Yuan, LU Cuifen, YANG Guichun, CHEN Zuxing. C₂-Symmetric Bisprolinamide Chiral Polymer Catalyst with Double Decker Silsesquioxane in Main Chain for the Asymmetric Aldol Reactions^†[J]. Chem. J. Chinese Universities, 2017, 38(11): 1968.

Figures/Tables 6

References 27

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Entry	Product	R₁	R₂	R₃	Yield^b(%)	e. e.^c(%)
1	5a	CH₃	H	Me	83	84.2^d
2	5b	Et	H	Me	65	83.8^d
3	5c	Ph	H	Me	52	82.0^d
4	5d	—(CH₂)₄—	—(CH₂)₄—	Me	60^e	80.1^f
5	5e	CH₃	H	Et	72	85.5^d

Entry	Product	R₁	R₂	R₃	Yield^b(%)	e. e.^c(%)
1	5a	CH₃	H	Me	83	84.2^d
2	5b	Et	H	Me	65	83.8^d
3	5c	Ph	H	Me	52	82.0^d
4	5d	—(CH₂)₄—	—(CH₂)₄—	Me	60^e	80.1^f
5	5e	CH₃	H	Et	72	85.5^d

Cycle	Yield^b(%)	e. e.^c(%)	Recovery rate(%)	Cycle	Yield^b(%)	e. e.^c(%)	Recovery rate(%)
1	83	84.2	89	4	82	82.2	91
2	82	82.5	92	5	80	82.8	89
3	81	84.7	92	6	77	82.0	87

Cycle	Yield^b(%)	e. e.^c(%)	Recovery rate(%)	Cycle	Yield^b(%)	e. e.^c(%)	Recovery rate(%)
1	83	84.2	89	4	82	82.2	91
2	82	82.5	92	5	80	82.8	89
3	81	84.7	92	6	77	82.0	87

C₂-Symmetric Bisprolinamide Chiral Polymer Catalyst with Double Decker Silsesquioxane in Main Chain for the Asymmetric Aldol Reactions^†

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Figures/Tables 6

References 27

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Entry	Additive	Loading(%)	Temperature/℃	Time/h	Yield^b(%)	e. e.^c(%)
1	HCOOH	15	0	18	83	84.2
2	CH₃COOH	15	0	18	56	47.4
3	C₆H₅COOH	15	0	18	87	48.3
4	ClCH₂COOH	15	0	18	31	63.9
5	Cl₂CHCOOH	15	0	18	None
6	F₃CCOOH	15	0	18	None
7	HCOOH	5	0	18	42	81.5
8	HCOOH	10	0	18	75	80.2
9	HCOOH	20	0	18	84	81.1
10	HCOOH	15	25	18	90	74.2
11	HCOOH	15	-25	18	32	84.7
12	HCOOH	15	0	8	31	82.6
13	HCOOH	15	0	32	86	80.5
14	HCOOH	15	0	48	91	83.5

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