NH4SCN-Promoted Formal [3＋3] Annulation for the Synthesis of 5-Arylated Pyrazolo[1,5-a]pyrimidines

doi:10.6023/cjoc202404017

Chinese Journal of Organic Chemistry ›› 2024, Vol. 44 ›› Issue (9): 2832-2840.DOI: 10.6023/cjoc202404017 Previous Articles Next Articles

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硫氰酸铵促进的[3＋3]环化反应合成5-芳基吡唑并[1,5-a]嘧啶

李龙龙^a, 何欣悦^a, 周龙生^a, 曲亨通^a, 冯承涛^a^,^*(), 徐坤^b^,^*()

a 安徽中医药大学药学院合肥 230012
b 北京工业大学化学与生命科学学院北京 100124

收稿日期:2024-04-11 修回日期:2024-05-07 发布日期:2024-05-23
通讯作者: 冯承涛, 徐坤
基金资助:
安徽省自然科学基金(2008085MB50); 及安徽省高校自然科学研究重点(KJ2021A0598)

NH₄SCN-Promoted Formal [3＋3] Annulation for the Synthesis of 5-Arylated Pyrazolo[1,5-a]pyrimidines

Longlong Li^a, Xinyue He^a, Longsheng Zhou^a, Hengtong Qu^a, Chengtao Feng^a(), Kun Xu^b()

a School of Pharmacy, Anhui University of Chinese Medicine, Hefei 230012
b College of Chemistry and Life Science, Beijing University of Technology, Beijing 100124

Received:2024-04-11 Revised:2024-05-07 Published:2024-05-23
Contact: Chengtao Feng, Kun Xu
Supported by:
Anhui Provincial Natural Science Foundation(2008085MB50); Education Bureau of Anhui Province(KJ2021A0598)

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Abstract

A formal [3＋3] annulation of 3-aminopyrazoles with cinnamaldehydes or cinnamyl alcohols mediated by NH₄SCN has been developed. This protocol provides a practical route to construct 5-arylated pyrazolo[1,5-a]pyrimidines with high functional group tolerance. The use of NH₄SCN as the cyanide anion surrogate allows the transient generation of cyanohydrin, which shifts the reactive center within cinnamaldehydes from formyl group to alkene group to realize an opposite regiocontrol comparing with previous reports.

Key words: tandem cyclization, hypervalent iodine, regioselectivity, pyrazolo[1,5-a]pyrimidine, cinnamaldehyde

Cite this article

Longlong Li, Xinyue He, Longsheng Zhou, Hengtong Qu, Chengtao Feng, Kun Xu. NH₄SCN-Promoted Formal [3＋3] Annulation for the Synthesis of 5-Arylated Pyrazolo[1,5-a]pyrimidines[J]. Chinese Journal of Organic Chemistry, 2024, 44(9): 2832-2840.

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Fig. & Tab. 7

References 16

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Entry	[CN]	Oxidant	Solvent	Yield^b^,^c/%
1	TMSCN	I₂O₅	DMSO	36 (13)
2	NH₄SCN	I₂O₅	DMSO	52 (10)
3	NaSCN	I₂O₅	DMSO	42 (14)
4	KSCN	I₂O₅	DMSO	41 (12)
5	NH₄SCN	NaIO₄	DMSO	40 (19)
6	NH₄SCN	TBHP	DMSO	0 (0)
7	NH₄SCN	—	DMSO	0 (0)
8	TMSCN	—	DMSO	0 (0)
9^d	NH₄SCN	I₂O₅	EtOH	Trace (trace)
10^d	NH₄SCN	I₂O₅	DMF	Trace (trace)
11^d	NH₄SCN	I₂O₅	CH₃CN	31 (8)
12^d^,^e	NH₄SCN	I₂O₅	DMSO	79 (9)
13^d^,^e^,^f	NH₄SCN	I₂O₅	DMSO	76 (11)
14^d^,^e^,^g	NH₄SCN	I₂O₅	DMSO	62 (13)
15^d^,^e	—	I₂O₅	DMSO	26 (18)
16^d^,^e^,^h	—	I₂O₅	DMSO	24 (13)

Entry	[CN]	Oxidant	Solvent	Yield^b^,^c/%
1	TMSCN	I₂O₅	DMSO	36 (13)
2	NH₄SCN	I₂O₅	DMSO	52 (10)
3	NaSCN	I₂O₅	DMSO	42 (14)
4	KSCN	I₂O₅	DMSO	41 (12)
5	NH₄SCN	NaIO₄	DMSO	40 (19)
6	NH₄SCN	TBHP	DMSO	0 (0)
7	NH₄SCN	—	DMSO	0 (0)
8	TMSCN	—	DMSO	0 (0)
9^d	NH₄SCN	I₂O₅	EtOH	Trace (trace)
10^d	NH₄SCN	I₂O₅	DMF	Trace (trace)
11^d	NH₄SCN	I₂O₅	CH₃CN	31 (8)
12^d^,^e	NH₄SCN	I₂O₅	DMSO	79 (9)
13^d^,^e^,^f	NH₄SCN	I₂O₅	DMSO	76 (11)
14^d^,^e^,^g	NH₄SCN	I₂O₅	DMSO	62 (13)
15^d^,^e	—	I₂O₅	DMSO	26 (18)
16^d^,^e^,^h	—	I₂O₅	DMSO	24 (13)

硫氰酸铵促进的[3＋3]环化反应合成5-芳基吡唑并[1,5-a]嘧啶

NH₄SCN-Promoted Formal [3＋3] Annulation for the Synthesis of 5-Arylated Pyrazolo[1,5-a]pyrimidines

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