吡啶桥连双功能有机催化剂催化二氧化碳、环氧化物和芳香胺合成3-芳基-2-噁唑烷酮的研究

doi:10.6023/cjoc201903030

摘要/Abstract

合成了一类羧基或羟基功能化的有机小分子催化剂, 成功用于二氧化碳、环氧化物和芳香胺一锅法制备噁唑烷酮类化合物的制备. 该催化体系具有反应条件温和、底物普适性好的优点. 控制实验表明整个反应过程经过了三个阶段: 环氧化物分别与二氧化碳、芳香胺反应形成环状碳酸酯、氨基醇, 最终环状碳酸酯和氨基醇进一步反应形成噁唑烷酮类化合物.

关键词: 有机催化剂, 二氧化碳, 噁唑烷酮, 环氧化物

A series of carboxyl group or hydroxyl group functionalized organocatalysts were synthesized and applied in three component reaction of carbon dioxide with epoxide, and aryl amines for the synthesis of 3-aryl-2-oxazolidinones. The method allows the reaction to proceed smoothly in the mild reaction conditions, together with excellent substrates scope of epoxides and aryl amines. The control experiments suggest that the cyclic carbonates are formed by the coupling of epoxides with carbon dioxide, which further react with the amino alcohol generated from epoxides and aryl amines, finally resulting in the desired products.

Key words: organocatalyst, carbon dioxide, oxazolidinones, epoxide

引用此文

刘铨瑶, 石磊, 刘宁. 吡啶桥连双功能有机催化剂催化二氧化碳、环氧化物和芳香胺合成3-芳基-2-噁唑烷酮的研究[J]. 有机化学, 2019, 39(10): 2882-2891.

Liu, Quanyao, Shi, Lei, Liu, Ning. Pyridine Bridged Organocatalyst for the Synthesis of 3-Aryl-2-oxazolidinones from Carbon Dioxide, Terminal Epoxide, and Aryl Amine[J]. Chinese Journal of Organic Chemistry, 2019, 39(10): 2882-2891.

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图/表 11

图式1. 有机催化剂的合成步骤

Scheme 1. Synthetic pathway of organocatalysts

Entry	Catalyst	Co-catalyst	Yield/%
1	1a	DBU	97
2	1b	DBU	75
3	1c	DBU	62
4	1d	DBU	92
5	1e	DBU	67
6	1f	DBU	89
7	1g	DBU	94
8	1h	DBU	71
9	1i	DBU	96
10	1j	DBU	99
11	1k	DBU	81
12	1l	DBU	67
13	1j	—	Trace
14	—	DBU	37

表1. 催化剂结构与催化性能研究a

Table 1. Structure-activity relationship of catalysts

Entry	1j/ mmol	DBU/ mmol	PO/ mL	CO₂/ kPa	Time/ h	Temp./ ℃	Yield/%
1	0.1	0.4	2	500	6	100	99
2	0.1	0.4	2	500	6	90	99
3	0.1	0.4	2	500	6	80	97
4	0.1	0.4	2	500	6	70	35
5	0.1	0.4	2	500	4	80	96
6	0.1	0.4	2	500	3	80	65
7	0.1	0.4	2	300	4	80	91
8	0.05	0.4	2	300	4	80	45
9	0.05	0.4	2	300	4	90	90
10	0.05	0.4	1.5	300	4	90	86
11	0.05	0.4	1	300	4	90	71
12	0.05	0.6	1	300	4	90	96
13	0.05	0.6	1	100	4	90	10

表2. 反应条件优化a

Table 2. Optimization of reaction condition

Table 3. Scope of substrates

图式2. 环氧丙烷和CO2的反应路线的探究

Scheme 2. Study on the reaction of PO with CO2

图式3. 环氧丙烷和苯胺的反应路线的探究

Scheme 3. Study on the reaction of PO with aniline

图式4. 碳酸丙烯酯和氨基醇的反应路线的探究

Scheme 4. Study on the reaction of PC with amino alcohol

图式5. 碳酸丙烯酯和苯胺的反应路线的探究

Scheme 5. Study on the reaction of PC with aniline

图1. 以CD3CN (0.5 mL)为氘代溶剂(a)苯胺(0.5 mmol)和(b) DBU (0.5 mmol)加入苯胺(0.5 mmol)的1H NMR图谱

Figure 1. 1H NMR spectra of only aniline (0.5 mmol) (a), and the mixture of aniline (0.5 mmol) and DBU (0.5 mmol) (b) in CD3CN (0.5 mL)

图2. 以CD3CN (0.5 mL)为氘代溶剂(a)氨基醇(0.5 mmol)和 (b) DBU (0.5 mmol)加入氨基醇(0.5 mmol)的1H NMR图谱

Figure 2. 1H NMR spectra of only amino alcohol (0.5 mmol) (a) and the mixture of amino alcohol (0.5 mmol) and DBU (0.5 mmol) (b) in CD3CN (0.5 mL)

图3. 有机催化剂和DBU协同催化的反应机理

Figure 3. Cooperative catalytic mechanism between organocatalyst and DBU

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