NEt3-Promoted Construction of Functionalized 4H-Chromenes via [4+2] Cycloaddition Reaction of ortho-Quinone Methides with β-Ketothioamides

doi:10.6023/cjoc202104005

Abstract

A novel and efficient method for the synthesis of highly substituted 4H-chromene derivatives by NEt₃-promoted annulation of β-ketothioamides (KTAs) and ortho-quinone methides (o-QMs) has been developed. This protocol involves a tandem sequence including 1,6-conjugate addition/O-cyclization/ring-opening/O-cyclization. This process exhibits good functional group tolerance, operationally-simple conditions and scalability.

Key words: ortho-quinone methide (o-QMs), β-ketothioamide, 4H-chromene derivative, [4+2] cycloaddition

Cite this article

Guangming Nan, Jingbo Zhan, Chunming Yuan, Lirong Wen, Ming Li. NEt₃-Promoted Construction of Functionalized 4H-Chromenes via [4+2] Cycloaddition Reaction of ortho-Quinone Methides with β-Ketothioamides[J]. Chinese Journal of Organic Chemistry, 2021, 41(9): 3682-3691.

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Entry	n(1a)∶n(2a)	Base (equiv.)	Solvent	T/℃	Yield/%
1	1∶1	NEt₃ (1)	EtOH	70	66
2	1∶1	—	EtOH	70	Trace
3	1∶1	DIPEA (1)	EtOH	70	60
4	1∶1	DABCO (1)	EtOH	70	57
5	1∶1	DBU (1)	EtOH	70	Trace
6	1∶1	DMAP (1)	EtOH	70	65
7	1∶1	Pyridine (1)	EtOH	70	35
8	1∶1	PPh₃ (1)	EtOH	70	32
9	1∶1	K₂CO₃ (1)	EtOH	70	Trace
10	1∶1	NEt₃ (0.5)	EtOH	70	77
11	1∶1	NEt₃ (0.2)	EtOH	70	72
12	1∶1	NEt₃ (0.5)	—	90	40
13	1∶1	NEt₃ (0.5)	HFIP	70	72
14	1∶1	NEt₃ (0.5)	CH₃OH	70	63
15	1∶1	NEt₃ (0.5)	TFE	70	65
16	1∶1	NEt₃ (0.5)	CH₃CN	70	65
17	1∶1	NEt₃ (0.5)	DCE	70	63
18	1∶1	NEt₃ (0.5)	THF	70	55
19	1∶1	NEt₃ (0.5)	Toluene	70	50
20	1∶1	NEt₃ (0.5)	EtOH	80	75
21	1∶1	NEt₃ (0.5)	EtOH	60	69
22	1∶1.2	NEt₃ (0.5)	EtOH	70	85
23	1.2∶1	NEt₃ (0.5)	EtOH	70	75
24	1∶1.5	NEt₃ (0.5)	EtOH	70	84
25^c	1∶1.2	NEt₃ (0.5)	EtOH	70	72

Entry	n(1a)∶n(2a)	Base (equiv.)	Solvent	T/℃	Yield/%
1	1∶1	NEt₃ (1)	EtOH	70	66
2	1∶1	—	EtOH	70	Trace
3	1∶1	DIPEA (1)	EtOH	70	60
4	1∶1	DABCO (1)	EtOH	70	57
5	1∶1	DBU (1)	EtOH	70	Trace
6	1∶1	DMAP (1)	EtOH	70	65
7	1∶1	Pyridine (1)	EtOH	70	35
8	1∶1	PPh₃ (1)	EtOH	70	32
9	1∶1	K₂CO₃ (1)	EtOH	70	Trace
10	1∶1	NEt₃ (0.5)	EtOH	70	77
11	1∶1	NEt₃ (0.2)	EtOH	70	72
12	1∶1	NEt₃ (0.5)	—	90	40
13	1∶1	NEt₃ (0.5)	HFIP	70	72
14	1∶1	NEt₃ (0.5)	CH₃OH	70	63
15	1∶1	NEt₃ (0.5)	TFE	70	65
16	1∶1	NEt₃ (0.5)	CH₃CN	70	65
17	1∶1	NEt₃ (0.5)	DCE	70	63
18	1∶1	NEt₃ (0.5)	THF	70	55
19	1∶1	NEt₃ (0.5)	Toluene	70	50
20	1∶1	NEt₃ (0.5)	EtOH	80	75
21	1∶1	NEt₃ (0.5)	EtOH	60	69
22	1∶1.2	NEt₃ (0.5)	EtOH	70	85
23	1.2∶1	NEt₃ (0.5)	EtOH	70	75
24	1∶1.5	NEt₃ (0.5)	EtOH	70	84
25^c	1∶1.2	NEt₃ (0.5)	EtOH	70	72

Compd.	R²	Yield/%
3ab	6-F	67
3ac	6-Cl	65
3ad	6-Br	68
3ae	6-CH₃	73
3af	6-OMe	76
3aq	8-OMe	78

Compd.	R²	Yield/%
3ab	6-F	67
3ac	6-Cl	65
3ad	6-Br	68
3ae	6-CH₃	73
3af	6-OMe	76
3aq	8-OMe	78

三乙胺促进的邻亚甲基苯醌与β-羰基硫代酰胺的[4+2]环加成反应构建功能化4H-色烯衍生物

NEt₃-Promoted Construction of Functionalized 4H-Chromenes via [4+2] Cycloaddition Reaction of ortho-Quinone Methides with β-Ketothioamides

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