炔基亚砜的分子内交叉偶联/[3,3]-硫鎓离子重排策略构建环烷并[c]呋喃

doi:10.6023/cjoc202507003

摘要/Abstract

报道了一种基于分子内串联重排反应的双环呋喃类化合物的合成策略. 该串联反应由三氟化硼乙醚络合物催化的炔基硫醚与炔基亚砜的分子内交叉偶联引发, 随后经历[3,3]-σ硫鎓离子重排及5-exo-dig环化反应, 最终以中等产率以及100%原子经济性获得产物环烷并[c]呋喃. 所得呋喃类化合物的合成应用价值已通过对产物中烷硫基和呋喃环的后修饰反应得到验证.

关键词: 3,3]-重排, 硫鎓离子, 杂环化, 环烷并[c]呋喃, 分子内反应

An intramolecular tandem rearrangement for the synthesis of bicyclic furans is reported. The reaction was initiated by an intramolecular cross-coupling of the built-in alkynyl sulfoxide and alkynyl sulfide motifs in the presence of BF₃•Et₂O, followed by a [3,3]-sigmatropic sulfonium rearrangement and 5-exo-dig cyclization, affording cycloalkano[c]furans as final products in moderate yields with 100% atom economy. The synthetic utility of the resulting furans has been demonstrated through late-stage diversification by utilizing the alkylthio groups or the furan rings.

Key words: 3,3]-rearrangement, sulfonium ion, heterocyclization, cycloalkano[c]furan, intramolecular reaction

引用此文

郭闻涛, 孟书玉, 王全瑞. 炔基亚砜的分子内交叉偶联/[3,3]-硫鎓离子重排策略构建环烷并[c]呋喃[J]. 有机化学, 2026, 46(2): 594-602.

Wentao Guo, Shuyu Meng, Quanrui Wang. Intramolecular Cross-Coupling/[3,3]-Sulfonium Rearrangement of Alkynyl Sulfoxides for the Construction of Cycloalkano[c]furans[J]. Chinese Journal of Organic Chemistry, 2026, 46(2): 594-602.

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Entry	c(1h)/(mol•L^－1)	Yield^b/%
Entry	c(1h)/(mol•L^－1)	6a	6a'
1	0.2	Trace	45
2	0.1	18	27
3	0.01	48	Trace
4	0.005	46	Trace

Entry	c(1h)/(mol•L^－1)	Yield^b/%
Entry	c(1h)/(mol•L^－1)	6a	6a'
1	0.2	Trace	45
2	0.1	18	27
3	0.01	48	Trace
4	0.005	46	Trace

Entry	Cat. (equiv.)	Solv.	T/℃	t/h	Conv.^b/%
1	BF₃•Et₂O (0.1)	DCE	70	2	50 (48)^c
2	BF₃•Et₂O (0.1)	DCE	70	6	52
3	BF₃•Et₂O (0.1)	DCE	70	12	57
4	BF₃•Et₂O (0.1)	DCE	25	6	46
5	BF₃•Et₂O (0.1)	DCE	25	12	49
6^d	BF₃•Et₂O (0.1)	DCE	70	12	65 (62)^c
7^d	BF₃•Et₂O (0.1)	DCE	70	12	35
8^d	BF₃•Et₂O (0.1)	DCE	70	12	29
9^d	BF₃•Et₂O (0.1)	DCE	70	12	27
10^d	TfOH (0.1)	DCE	70	12	43
11^d	Tf₂NH (0.1)	DCE	70	6	41
12^d	AgSbF₆ (0.1)	DCE	70	6	26
13^d	TiCl₄ (0.1)	DCE	70	12	13
14^d	AuCl₃ (0.1)	DCE	70	12	18
15^d	SnCl₄ (0.1)	DCE	70	12	31
16^d	In(OTf)₃ (0.1)	DCE	70	12	28
17^d	Eu(OTf)₃ (0.1)	DCE	70	12	35
18^d	SmI₂ (0.1)	DCE	70	12	<5
19^d	BuBOTf (0.1)	DCE	70	12	41
20^d	BF₃•Et₂O (0.1)	Toluene	70	6	32
21^d	BF₃•Et₂O (0.1)	MeCN	70	8	41
22^d	BF₃•Et₂O (0.1)	MeNO₂	70	4	27
23^d	BF₃•Et₂O (0.1)	CCl₄	70	12	46

Entry	Cat. (equiv.)	Solv.	T/℃	t/h	Conv.^b/%
1	BF₃•Et₂O (0.1)	DCE	70	2	50 (48)^c
2	BF₃•Et₂O (0.1)	DCE	70	6	52
3	BF₃•Et₂O (0.1)	DCE	70	12	57
4	BF₃•Et₂O (0.1)	DCE	25	6	46
5	BF₃•Et₂O (0.1)	DCE	25	12	49
6^d	BF₃•Et₂O (0.1)	DCE	70	12	65 (62)^c
7^d	BF₃•Et₂O (0.1)	DCE	70	12	35
8^d	BF₃•Et₂O (0.1)	DCE	70	12	29
9^d	BF₃•Et₂O (0.1)	DCE	70	12	27
10^d	TfOH (0.1)	DCE	70	12	43
11^d	Tf₂NH (0.1)	DCE	70	6	41
12^d	AgSbF₆ (0.1)	DCE	70	6	26
13^d	TiCl₄ (0.1)	DCE	70	12	13
14^d	AuCl₃ (0.1)	DCE	70	12	18
15^d	SnCl₄ (0.1)	DCE	70	12	31
16^d	In(OTf)₃ (0.1)	DCE	70	12	28
17^d	Eu(OTf)₃ (0.1)	DCE	70	12	35
18^d	SmI₂ (0.1)	DCE	70	12	<5
19^d	BuBOTf (0.1)	DCE	70	12	41
20^d	BF₃•Et₂O (0.1)	Toluene	70	6	32
21^d	BF₃•Et₂O (0.1)	MeCN	70	8	41
22^d	BF₃•Et₂O (0.1)	MeNO₂	70	4	27
23^d	BF₃•Et₂O (0.1)	CCl₄	70	12	46