Study of BF3•Et2O-Promoted Rearrangement of Cyclopropenylcarbinols

doi:10.6023/cjoc202405015

Abstract

γ-Ylidenebutenolides and benzofulvenes are of considerable importance in natural product and medicinal chemistry. Cyclopropenylcarbinols were promoted by BF₃•Et₂O to induce the C—C bond cleavage reaction of cyclopropenes via dehydroxylation to form an allene carbocation intermediate. This leads to the construction of γ-ylidenebutenolide and benzofulvene compounds in one pot via different isomerization rearrangement paths. This synthetic strategy expands the synthesis methods of two types of compounds, achieving a total yield of 68%~99%. In addition, the electronic effect and reaction temperature considerably influence the ratio of the two compounds. Moreover, the reaction provides a new method for precise C—C bond cleavage of cyclopropenes.

Key words: cyclopropene, BF₃•Et₂O, γ-alkylidenebutenolide, benzofulvene, C—C bond cleavage

Cite this article

Miaomiao Xun, Jingjing Guo, Wenbing Ma, Yuqiang Li, Changchun Yuan, Kai Fu. Study of BF₃•Et₂O-Promoted Rearrangement of Cyclopropenylcarbinols[J]. Chinese Journal of Organic Chemistry, 2024, 44(9): 2760-2776.

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Fig. & Tab. 7

References 24

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Entry	Acid (equiv.)	Solvent	T/℃	Yield/%			Ratio 2a/3a
Entry	Acid (equiv.)	Solvent	T/℃	2a	3a	Total	Ratio 2a/3a
1	CH₃SO₃H (1.0)	Toluene	r.t.	36	28	64	1.3/1
2	p-TsOH (1.0)	Toluene	r.t. to 100	41	38	79	1.1/1
3	Cu(OTf)₂ (2.0)	Toluene	r.t. to 50	40	28	68	1.4/1
4	Yb(OTf)₃ (2.0)	Toluene	r.t. to 100	45	37	82	1.2/1
5	In(OTf)₃ (1.0)	Toluene	r.t.	49	35	84	1.4/1
6	Hf(OTf)₄ (1.0)	Toluene	r.t.	47	34	82	1.4/1
7	TiCl₄ (1.0)	Toluene	r.t.	35	37	72	0.9/1
8	FeCl₃ (1.0)	Toluene	r.t.	41	38	79	1.1/1
9	AlCl₃ (1.0)	Toluene	r.t.	50	30	80	1.7/1
10	BF₃•OEt₂ (1.0)	Toluene	r.t.	50	37	87	1.4/1
11^b	BF₃•OEt₂ (5.0)	Toluene	－78	—	—	—	—
12	BF₃•OEt₂ (5.0)	Toluene	－60	59	33	92	1.8/1
13	BF₃•OEt₂ (3.0)	Toluene	－40	59	33	92	1.8/1
14	BF₃•OEt₂ (1.5)	Toluene	0	50	33	83	1.5/1
15	BF₃•OEt₂ (1.0)	Toluene	60	51	36	87	1.4/1
16^b	BF₃•OEt₂(3.0)	THF	－40 or r.t.	—	—	—	—
17	BF₃•OEt₂(3.0)	THF	50	21	19	40	1.1/1
18	BF₃•OEt₂(3.0)	DCM	－40	53	34	87	1.6/1
19	BF₃•OEt₂(3.0)	DCE	－35	52	36	88	1.4/1
20	BF₃•OEt₂(3.0)	EA	－40 to r.t.	50	26	76	1.9/1
21	BF₃•OEt₂(3.0)	n-Hexane	r.t.	41	38	79	1.1/1
22^c	BF₃•OEt₂ (3.0)	Toluene	－40	60	33	93	1.8/1

Entry	Acid (equiv.)	Solvent	T/℃	Yield/%			Ratio 2a/3a
Entry	Acid (equiv.)	Solvent	T/℃	2a	3a	Total	Ratio 2a/3a
1	CH₃SO₃H (1.0)	Toluene	r.t.	36	28	64	1.3/1
2	p-TsOH (1.0)	Toluene	r.t. to 100	41	38	79	1.1/1
3	Cu(OTf)₂ (2.0)	Toluene	r.t. to 50	40	28	68	1.4/1
4	Yb(OTf)₃ (2.0)	Toluene	r.t. to 100	45	37	82	1.2/1
5	In(OTf)₃ (1.0)	Toluene	r.t.	49	35	84	1.4/1
6	Hf(OTf)₄ (1.0)	Toluene	r.t.	47	34	82	1.4/1
7	TiCl₄ (1.0)	Toluene	r.t.	35	37	72	0.9/1
8	FeCl₃ (1.0)	Toluene	r.t.	41	38	79	1.1/1
9	AlCl₃ (1.0)	Toluene	r.t.	50	30	80	1.7/1
10	BF₃•OEt₂ (1.0)	Toluene	r.t.	50	37	87	1.4/1
11^b	BF₃•OEt₂ (5.0)	Toluene	－78	—	—	—	—
12	BF₃•OEt₂ (5.0)	Toluene	－60	59	33	92	1.8/1
13	BF₃•OEt₂ (3.0)	Toluene	－40	59	33	92	1.8/1
14	BF₃•OEt₂ (1.5)	Toluene	0	50	33	83	1.5/1
15	BF₃•OEt₂ (1.0)	Toluene	60	51	36	87	1.4/1
16^b	BF₃•OEt₂(3.0)	THF	－40 or r.t.	—	—	—	—
17	BF₃•OEt₂(3.0)	THF	50	21	19	40	1.1/1
18	BF₃•OEt₂(3.0)	DCM	－40	53	34	87	1.6/1
19	BF₃•OEt₂(3.0)	DCE	－35	52	36	88	1.4/1
20	BF₃•OEt₂(3.0)	EA	－40 to r.t.	50	26	76	1.9/1
21	BF₃•OEt₂(3.0)	n-Hexane	r.t.	41	38	79	1.1/1
22^c	BF₃•OEt₂ (3.0)	Toluene	－40	60	33	93	1.8/1

Entry	Substrate 1							T/℃	Product 2 and yield						Product 3 and yield					Total				Ratio 2/3
1								－40												93%				1.8/1
1	1a							－40	2a, 60%						3a, 33%					93%				1.8/1
2								－40												85%				1.9/1
2	1b							－40	2a, 56%						3b, 29%					85%				1.9/1
3								－40												89%				1.5/1
3	1c							－40	2a, 54%						3c, 35%					89%				1.5/1
4								－40												86%				1.9/1
4	1d							－40	2d, 56%						3d, 30%					86%				1.9/1
5^b								－40												86%				1/1.5
5^b	1e							－40	2e, 34%						3e, 52%					86%				1/1.5
6								－40												86%				1.9/1
6	1f							－40	2f, 56%						3f, 30%					86%				1.9/1
Entry			Substrate 1		T/℃					Product 2 and yield						Product 3 and yield		Total					Ratio 2/3
7^b					－40													78%					1/2.9
7^b			1g		－40					2g, 20%						3g, 58%		78%					1/2.9
8					－40													90%					1.6/1
8			1h		－40					2h, 56%						3h, 34%		90%					1.6/1
9^b					－40													75%					1/2.9
9^b			1i		－40					2i, 19%						3i, 56%		75%					1/2.9
10					－40													88%					2.8/1
10			1j		－40					2j, 65%						3j, 23%		88%					2.8/1
11					－40													95%					1/2.1
11			1k		－40					2k, 31%						3k, 64%		95%					1/2.1
12					－40													90%					1/1.8
12			1l		－40					2l, 32%						3l, 58%		90%					1/1.8
13^b					－20													72%					1/1.4
13^b			1m		－20					2m, 30%						3m, 42%		72%					1/1.4
Entry		Substrate 1					T/℃				Product 2 and yield			Product 3 and yield			Total					Ratio 2/3
14							－40										68%					1.1/1
14		1n					－40				2n, 36%			3n, 32%			68%					1.1/1
15^b^,^c							－40										74%					1/2.9
15^b^,^c		1o					－40				2o, 19%			3o, 55%			74%					1/2.9
16							－40										89%					1/6.4
16		1p					－40				2p, 12%			3p, 77%			89%					1/6.4
17							r.t.										94%					3.7/1
17		1q					r.t.				2q, 74%			3q, 20%			94%					3.7/1
18							－40										83%					2.8/1
18		1r					－40				2r, 61%			3r, 22%			83%					2.8/1
19							－40										85%					1/1
19		1s					－40				2s, 42%			3s, 43%			85%					1/1
20							－40										94%					1/1.2
20		1t					－40				2t, 43%			3t, 51%			94%					1/1.2
Entry				Substrate 1		T/℃						Product 2 and yield	Product 3 and yield						Total		Ratio 2/3
21						－40													90%		2.6/1
21				1u		－40						2u, 65%	3u, 25%						90%		2.6/1
22						0													93%		2.3/1
22				1v		0						2v, 65%	3v, 28%						93%		2.3/1
23						0													94%		4.5/1
23				1w		0						2w, 77%	3w, 17%						94%		4.5/1
24						－20													99%		2.9/1
24				1x		－20						2x, 74%	3x, 25%						99%		2.9/1
25						－40													90%		1/1.4
25				1y		－40						2y, 37%	3y, 53%						90%		1/1.4

Entry	Substrate 1							T/℃	Product 2 and yield						Product 3 and yield					Total				Ratio 2/3
1								－40												93%				1.8/1
1	1a							－40	2a, 60%						3a, 33%					93%				1.8/1
2								－40												85%				1.9/1
2	1b							－40	2a, 56%						3b, 29%					85%				1.9/1
3								－40												89%				1.5/1
3	1c							－40	2a, 54%						3c, 35%					89%				1.5/1
4								－40												86%				1.9/1
4	1d							－40	2d, 56%						3d, 30%					86%				1.9/1
5^b								－40												86%				1/1.5
5^b	1e							－40	2e, 34%						3e, 52%					86%				1/1.5
6								－40												86%				1.9/1
6	1f							－40	2f, 56%						3f, 30%					86%				1.9/1
Entry			Substrate 1		T/℃					Product 2 and yield						Product 3 and yield		Total					Ratio 2/3
7^b					－40													78%					1/2.9
7^b			1g		－40					2g, 20%						3g, 58%		78%					1/2.9
8					－40													90%					1.6/1
8			1h		－40					2h, 56%						3h, 34%		90%					1.6/1
9^b					－40													75%					1/2.9
9^b			1i		－40					2i, 19%						3i, 56%		75%					1/2.9
10					－40													88%					2.8/1
10			1j		－40					2j, 65%						3j, 23%		88%					2.8/1
11					－40													95%					1/2.1
11			1k		－40					2k, 31%						3k, 64%		95%					1/2.1
12					－40													90%					1/1.8
12			1l		－40					2l, 32%						3l, 58%		90%					1/1.8
13^b					－20													72%					1/1.4
13^b			1m		－20					2m, 30%						3m, 42%		72%					1/1.4
Entry		Substrate 1					T/℃				Product 2 and yield			Product 3 and yield			Total					Ratio 2/3
14							－40										68%					1.1/1
14		1n					－40				2n, 36%			3n, 32%			68%					1.1/1
15^b^,^c							－40										74%					1/2.9
15^b^,^c		1o					－40				2o, 19%			3o, 55%			74%					1/2.9
16							－40										89%					1/6.4
16		1p					－40				2p, 12%			3p, 77%			89%					1/6.4
17							r.t.										94%					3.7/1
17		1q					r.t.				2q, 74%			3q, 20%			94%					3.7/1
18							－40										83%					2.8/1
18		1r					－40				2r, 61%			3r, 22%			83%					2.8/1
19							－40										85%					1/1
19		1s					－40				2s, 42%			3s, 43%			85%					1/1
20							－40										94%					1/1.2
20		1t					－40				2t, 43%			3t, 51%			94%					1/1.2
Entry				Substrate 1		T/℃						Product 2 and yield	Product 3 and yield						Total		Ratio 2/3
21						－40													90%		2.6/1
21				1u		－40						2u, 65%	3u, 25%						90%		2.6/1
22						0													93%		2.3/1
22				1v		0						2v, 65%	3v, 28%						93%		2.3/1
23						0													94%		4.5/1
23				1w		0						2w, 77%	3w, 17%						94%		4.5/1
24						－20													99%		2.9/1
24				1x		－20						2x, 74%	3x, 25%						99%		2.9/1
25						－40													90%		1/1.4
25				1y		－40						2y, 37%	3y, 53%						90%		1/1.4

BF₃•Et₂O促进的环丙烯基甲醇衍生物重排反应研究

Study of BF₃•Et₂O-Promoted Rearrangement of Cyclopropenylcarbinols

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BF3•Et2O促进的环丙烯基甲醇衍生物重排反应研究