Brønsted碱促进的β-(2-羟基芳基)乙烯磺酰氟与β,γ-不饱和酮酯(炔酮)串联环化反应合成多取代4H-色烯

doi:10.6023/cjoc202404037

有机化学 ›› 2024, Vol. 44 ›› Issue (11): 3365-3374.DOI: 10.6023/cjoc202404037 上一篇下一篇

研究论文

Brønsted碱促进的β-(2-羟基芳基)乙烯磺酰氟与β,γ-不饱和酮酯(炔酮)串联环化反应合成多取代4H-色烯

唐德林, 罗锦昀, 杜广芬^*(), 蔡志华, 何林^*()

石河子大学化学化工学院新疆石河子 832000

收稿日期:2024-05-22 修回日期:2024-06-08 发布日期:2024-07-10
基金资助:
国家自然科学基金(21662029); 石河子大学国际合作(GJHZ202204)

Synthesis of Multisubstituted 4H-Chromenes via Brønsted Base- Mediated Tandem Cyclization Reactions of β-(2-Hydroxyaryl) Ethenesulfonyl Fluorides and β,γ-Unsaturated Ketoesters (Ynones)

Delin Tang, Jinyun Luo, Guangfen Du^*(), Zhihua Cai, Lin He^*()

School of Chemistry and Chemical Engineering, Shihezi University, Shihezi, Xinjiang 832000

Received:2024-05-22 Revised:2024-06-08 Published:2024-07-10
Contact: *E-mail:duguangfen@shzu.edu.cn;helin@shzu.edu.cn
Supported by:
National Natural Science Foundation of China(21662029); International Cooperation Project of Shihezi University(GJHZ202204)

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摘要/Abstract

在20 mol% Cs₂CO₃催化下, β-(2-羟基芳基)乙烯磺酰氟与炔酮酯在室温下发生分子间/分子内Michael加成反应, 以56%~70%的产率获得11种含磺酰氟基团的多取代4H-色烯衍生物. 此外, 在50 mol% Cs₂CO₃促进下, β-(2-羟基芳基)乙烯磺酰氟与炔酮在50 ℃下发生类似的串联反应, 以25%~80%的产率得到12种多取代的4H-色烯衍生物.

关键词: β-(2-羟基芳基)乙烯磺酰氟, β,γ-不饱和酮酯(炔酮), 4H-色烯

Under the catalysis of 20 mol% Cs₂CO₃, β-(2-hydroxyaryl) ethenesulfonyl fluorides reacted with ketoesters throu- gh a tandem intermolecular/intramolecular Michael addition process at room temperature, affording 11 multisubstituted 4H- chromenes bearing a useful sulfonyl fluoride groups in 56%~70% yields. In addition, under the mediation of 50 mol% Cs₂CO₃, β-(2-hydroxyaryl) ethenesulfonyl fluorides couple with ynones through a similar tandem process at 50 ℃, giving 12 multisubstituted 4H-chromenes in 25%~80% yields.

Key words: β-(2-hydroxyaryl) ethenesulfonyl fluorides, β,γ-unsaturated ketoesters (ynones), 4H-chromenes

引用此文

唐德林, 罗锦昀, 杜广芬, 蔡志华, 何林. Brønsted碱促进的β-(2-羟基芳基)乙烯磺酰氟与β,γ-不饱和酮酯(炔酮)串联环化反应合成多取代4H-色烯[J]. 有机化学, 2024, 44(11): 3365-3374.

Delin Tang, Jinyun Luo, Guangfen Du, Zhihua Cai, Lin He. Synthesis of Multisubstituted 4H-Chromenes via Brønsted Base- Mediated Tandem Cyclization Reactions of β-(2-Hydroxyaryl) Ethenesulfonyl Fluorides and β,γ-Unsaturated Ketoesters (Ynones)[J]. Chinese Journal of Organic Chemistry, 2024, 44(11): 3365-3374.

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图/表 8

图式1. 含色烯结构和SO2F官能团的药物活性分子

Scheme 1. Pharmaceutically active molecules containing chromene structures and SO2F functional groups

图式2. 4H-色烯的合成

Scheme 2. Synthesis of 4H-chromenes

Entry	Catalyst	Solvent	Yield^b/%
1	Na₂CO₃	CH₃CN	36
2	K₂CO₃	CH₃CN	42
3	Cs₂CO₃	CH₃CN	55
4	Na₂HPO₄	CH₃CN	NR
5	K₃PO₄	CH₃CN	47
6	NaOH	CH₃CN	48
7	Et₃N	CH₃CN	18
8	DIPEA	CH₃CN	17
9	DABCO	CH₃CN	Trace
10	DBU	CH₃CN	15
11	TBD	CH₃CN	23
12	TMG	CH₃CN	Trace
13	^tBuOK	CH₃CN	46
14^c	—	CH₃CN	nr
15	Cs₂CO₃	DME	51
16	Cs₂CO₃	THF	31
17	Cs₂CO₃	1,4-Dioxane	39
18	Cs₂CO₃	DMSO	13
19	Cs₂CO₃	Acetone	Trace
20	Cs₂CO₃	DCE	14
21	Cs₂CO₃	Toluene	10
22^d	Cs₂CO₃	CH₃CN	47
23^e	Cs₂CO₃	CH₃CN	53
24^f	Cs₂CO₃	CH₃CN	48
25^g	Cs₂CO₃	CH₃CN	67
26^h	Cs₂CO₃	CH₃CN	45
27ⁱ	Cs₂CO₃	CH₃CN	47
28^j	Cs₂CO₃	CH₃CN	60

表1. 反应条件的优化a

Table 1. Optimization of reaction conditions

表2. β,γ-不饱和酮酯和β-(2-羟基苯基)乙烯磺酰氟底物范围a

Table 2. Substrate scope of β,γ-unsaturated ketoesters and β-(2-hydroxyphenyl) ethenesulfonyl fluorides

表3. 炔酮底物范围a

Table 3. Substrate scope of ynones

图式3. 克级放大反应

Scheme 3. Gram-scale reaction

图式4. 1a与2a的反应机理探究实验

Scheme 4. Reaction mechanism investigation experiments for 1a and 2a

图式5. 可能的反应机理

Scheme 5. Possible reaction mechanism

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Brønsted碱促进的β-(2-羟基芳基)乙烯磺酰氟与β,γ-不饱和酮酯(炔酮)串联环化反应合成多取代4H-色烯

Synthesis of Multisubstituted 4H-Chromenes via Brønsted Base- Mediated Tandem Cyclization Reactions of β-(2-Hydroxyaryl) Ethenesulfonyl Fluorides and β,γ-Unsaturated Ketoesters (Ynones)

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