Synthesis of 2,3-Disubstituted Dihydrobenzofurans from o-Quinone Methides and Sulfur Ylides

doi:10.6023/cjoc202307019

Abstract

A facile and efficient approach to dihydrobenzofurans from sulfur ylides and o-quinone methides (o-QMs) was developed. In most cases, the reaction could be completed in the presence of N,N-diisopropylethylamine (DIPEA) in CH₂Cl₂ at room temperature within 1 h, providing trans-2,3-disubstitiuted dihydrobenzofurans in good to excellent yields. The reaction could expand to a scale of grams, and the products could be converted into the potentially bioactive benzofuran derivatives. The plausible mechanism is proposed.

Key words: dihydrobenzofuran, o-quinone methides, sulfur ylide, [4＋1] cycloaddition, base-catalysis

Cite this article

Mengzhu Li, Boying Meng, Wenjie Lan, Bin Fu. Synthesis of 2,3-Disubstituted Dihydrobenzofurans from o-Quinone Methides and Sulfur Ylides[J]. Chinese Journal of Organic Chemistry, 2024, 44(1): 195-203.

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Entry	Solvent	Base	T/℃	Time/h	Yield^b/%
1	CH₃CN	K₂CO₃	r.t.	6	75
2	THF	K₂CO₃	r.t.	6	85
3	CHCl₃	K₂CO₃	r.t.	6	86
4	CH₂Cl₂	K₂CO₃	r.t.	6	91
5	Dioxane	K₂CO₃	r.t.	12	68
6	Acetone	K₂CO₃	r.t.	16	73
7	Toluene	K₂CO₃	r.t.	24	85
8	CH₃OH	K₂CO₃	r.t.	24	—
9	CH₂Cl₂	Li₂CO₃	r.t.	6	93
10	CH₂Cl₂	Na₂CO₃	r.t.	6	89
11	CH₂Cl₂	Cs₂CO₃	r.t.	12	91
12	CH₂Cl₂	t-BuOK	r.t.	12	30
13	CH₂Cl₂	Et₃N	r.t.	1	85
14	CH₂Cl₂	DIEPA	r.t.	1	97
15	CH₂Cl₂	DIEPA	0	6	83
16	CH₂Cl₂	DIEPA	40	1	90

Entry	Solvent	Base	T/℃	Time/h	Yield^b/%
1	CH₃CN	K₂CO₃	r.t.	6	75
2	THF	K₂CO₃	r.t.	6	85
3	CHCl₃	K₂CO₃	r.t.	6	86
4	CH₂Cl₂	K₂CO₃	r.t.	6	91
5	Dioxane	K₂CO₃	r.t.	12	68
6	Acetone	K₂CO₃	r.t.	16	73
7	Toluene	K₂CO₃	r.t.	24	85
8	CH₃OH	K₂CO₃	r.t.	24	—
9	CH₂Cl₂	Li₂CO₃	r.t.	6	93
10	CH₂Cl₂	Na₂CO₃	r.t.	6	89
11	CH₂Cl₂	Cs₂CO₃	r.t.	12	91
12	CH₂Cl₂	t-BuOK	r.t.	12	30
13	CH₂Cl₂	Et₃N	r.t.	1	85
14	CH₂Cl₂	DIEPA	r.t.	1	97
15	CH₂Cl₂	DIEPA	0	6	83
16	CH₂Cl₂	DIEPA	40	1	90

Entry	R²	Product	Time/h	Yield^b/%	dr^c
1	4-ClC₆H₄	3ab	1	88	>19∶1
2	4-BrC₆H₄	3ac	1	80	>19∶1
3	4-CNC₆H₄	3ad	1	89	>19∶1
4	4-CF₃C₆H₄	3ae	1	86	>19∶1
5	4-CH₃C₆H₄	3af	1	98	>19∶1
6	3-MeOC₆H₄	3ag	1	87	>19∶1
7	3-FC₆H₄	3ah	1	75	>19∶1
8	3-O₂NC₆H₄	3ai	1	96	>19∶1
9	2-FC₆H₄	3aj	1	81	>19∶1
10	2-HOC₆H₄	3ak	1	92	>19∶1
11	2-Naphthyl	3al	1	83	>19∶1
12	2-Furyl	3am	6	78	>19∶1
13	2-Thienyl	3an	8	87	>19∶1
14	Cyclopropyl	3ao	1	80	>19∶1
15	t-Bu	3ap	1	87	>19∶1
16	Adamantyl	3aq	1	81	>19∶1

Entry	R²	Product	Time/h	Yield^b/%	dr^c
1	4-ClC₆H₄	3ab	1	88	>19∶1
2	4-BrC₆H₄	3ac	1	80	>19∶1
3	4-CNC₆H₄	3ad	1	89	>19∶1
4	4-CF₃C₆H₄	3ae	1	86	>19∶1
5	4-CH₃C₆H₄	3af	1	98	>19∶1
6	3-MeOC₆H₄	3ag	1	87	>19∶1
7	3-FC₆H₄	3ah	1	75	>19∶1
8	3-O₂NC₆H₄	3ai	1	96	>19∶1
9	2-FC₆H₄	3aj	1	81	>19∶1
10	2-HOC₆H₄	3ak	1	92	>19∶1
11	2-Naphthyl	3al	1	83	>19∶1
12	2-Furyl	3am	6	78	>19∶1
13	2-Thienyl	3an	8	87	>19∶1
14	Cyclopropyl	3ao	1	80	>19∶1
15	t-Bu	3ap	1	87	>19∶1
16	Adamantyl	3aq	1	81	>19∶1

Entry	R¹	Product	Time/h	Yield^b/%	dr^c
1	Ph	3ba	1	55	>19∶1
2	4-CH₃C₆H₄	3ca	1	68	>19∶1
3	4-MeOC₆H₄	3da	12	67	>19∶1
4	4-FC₆H₄	3ea	1	85	>19∶1
5	4-ClC₆H₄	3fa	1	85	>19∶1
6	4-BrC₆H₄	3ga	1	83	>19∶1
7	3-MeC₆H₄	3ha	1	68	>19∶1
8	2-MeOC₆H₄	3ia	12	52	>19∶1
9	2-Thienyl	3ja	1	24	>19∶1

邻亚甲醌与硫叶立德反应合成2,3-二取代苯并二氢呋喃化合物