Brønsted Acid-Catalyzed Intramolecular Hydroalkoxylation/Claisen Rearrangement of Ynamides★

doi:10.6023/A23040188

Acta Chimica Sinica ›› 2023, Vol. 81 ›› Issue (9): 1101-1107.DOI: 10.6023/A23040188 Previous Articles Next Articles

Special Issue: 庆祝《化学学报》创刊90周年合辑

Communication

Brønsted酸催化炔酰胺分子内氢烷氧化/Claisen重排反应^★

翟彤仪^a, 葛畅^a, 钱鹏程^b^,^*(), 周波^a, 叶龙武^a^,^c^,^*()

a 厦门大学化学化工学院厦门 361005
b 温州大学化学与材料工程学院温州 325035
c 中国科学院上海有机化学研究所金属有机化学国家重点实验室上海 200032

投稿日期:2023-04-30 发布日期:2023-06-13
作者简介:
^★庆祝《化学学报》创刊90周年.
基金资助:
国家自然科学基金(22125108); 国家自然科学基金(22121001); 厦门大学校长基金(20720210002); 及国家基础科学人才培养基金(J1310024)

Brønsted Acid-Catalyzed Intramolecular Hydroalkoxylation/Claisen Rearrangement of Ynamides^★

Tongyi Zhai^a, Chang Ge^a, Pengcheng Qian^b(), Bo Zhou^a, Longwu Ye^a^,^c()

a College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005
b College of Chemistry & Materials Engineering, Wenzhou University, Wenzhou 325035
c State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032

Received:2023-04-30 Published:2023-06-13
Contact: *E-mail: qpc@wzu.edu.cn; longwuye@xmu.edu.cn; Tel.: 0592-2185833
About author:
^★Dedicated to the 90th anniversary of Acta Chimica Sinica.
Supported by:
The National Natural Science Foundation of China(22125108); The National Natural Science Foundation of China(22121001); The President Research Funds from Xiamen University(20720210002); The National Found for Fostering Talents of Basic Science (NFFTBS(J1310024)

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Abstract

A Brønsted acid-catalyzed intramolecular hydroalkoxylation/Claisen rearrangement of ynamides for the synthesis of eight-membered lactams is presented. Firstly, the keteniminium intermediate was generated from the activation of ynamide by Brønsted acid, which could interact with intramolecular hydroxy group through hydrogen bonding and ion pairing effects. Then, the tandem hydroalkoxylation/Claisen rearrangement took place and produced eight-membered lactams. Meanwhile, preliminary studies were conducted into the chiral Brønsted acid-catalyzed kinetic resolution, and several chiral eight-membered lactams were successfully synthesized. Other notable features of this metal-free method include the simple procedure, mild reaction conditions and good functional group compatibility. This research provides a practical method for the synthesis of biologically important eight-membered lactam skeletons. Accordingly, MsOH (5 mol%, 0.005 mmol, 0.32 μL) was added to the solution of ynamide (1 equiv., 0.1 mmol) in dry PhCl (4 mL) at room temperature. The reaction mixture was then stirred at 60 ℃ and the progress of the reaction was monitored by thin layer chromatography (TLC). Upon completion, the reaction was quenched with Et₃N (0.005 mmol, 0.7 μL), concentrated and purified by chromatography on silica gel (eluent: petroleum ether/ethyl acetate, V∶V=5∶1), to afford the desired eight-membered lactam. Under this condition, a series of ynamides with different substituents worked smoothly to provide the corresponding eight-membered lactams efficiently. Furthermore, chiral Brønsted acid (10 mol%, 0.005 mmol, 3.5 mg) and H₂O (0.05 mmol, 0.9 μL) were added to the solution of ynamide (1 equiv., 0.05 mmol) in PhCl (2 mL) at –20 ℃ and the progress of the reaction was monitored by TLC. Upon completion, the reaction was quenched with Et₃N (0.005 mmol, 0.75 μL), concentrated and purified by chromatography on silica gel (eluent: petroleum ether/ethyl acetate, V∶V=5∶1), to afford the chiral eight-membered lactam and chiral substrate. Also, a plausible mechanism involving the hydrogen bonding and ion pairing effects is proposed based on experimental results.

Key words: ynamide, Brønsted acid catalysis, Claisen rearrangement, medium-sized lactam, kinetic resolution

Cite this article

Tongyi Zhai, Chang Ge, Pengcheng Qian, Bo Zhou, Longwu Ye. Brønsted Acid-Catalyzed Intramolecular Hydroalkoxylation/Claisen Rearrangement of Ynamides^★[J]. Acta Chimica Sinica, 2023, 81(9): 1101-1107.

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Fig. & Tab. 7

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Entry	(–)-2	(–)-1	s factor
1			22.7
2			7.6
3			29.6

Entry	(–)-2	(–)-1	s factor
1			22.7
2			7.6
3			29.6

Brønsted酸催化炔酰胺分子内氢烷氧化/Claisen重排反应^★

Brønsted Acid-Catalyzed Intramolecular Hydroalkoxylation/Claisen Rearrangement of Ynamides^★

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Entry	Catalyst	Conditions	Yield^b/%
1	TfOH	PhCl, 40 ℃, 24 h	50
2	TsOH	PhCl, 40 ℃, 24 h	51
3	MsOH	PhCl, 40 ℃, 24 h	80
4	(PhO)₂P(O)OH	PhCl, 40 ℃, 24 h	40
5	(PhO)₂P(O)NHTf	PhCl, 40 ℃, 24 h	78
6	A1	PhCl, 40 ℃, 24 h	60
7	A2	PhCl, 40 ℃, 24 h	22
8	MsOH	PhCl, 60 ℃, 24 h	99
9	MsOH	PhMe, 60 ℃, 24 h	24
10	MsOH	DCE, 60 ℃, 24 h	34
11	MsOH	THF, 60 ℃, 24 h	91
12	MsOH	1,4-dioxane, 60 ℃, 24 h	97

Entry	Time/h	Yield^b/%
1	24	99
2	48	99
3	48	94
4	48	99
5	48	99
6	12	58
7	74	86
8^c	30	99
9	53	99
10	48	80
11	48	86
12^c	30	42
13^c	30	98
14	48	99
15	24	99
16	48	90
17	35	55
18	24	88

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Brønsted酸催化炔酰胺分子内氢烷氧化/Claisen重排反应★

Brønsted Acid-Catalyzed Intramolecular Hydroalkoxylation/Claisen Rearrangement of Ynamides★

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Abstract

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Fig. & Tab. 7

References 11

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Brønsted酸催化炔酰胺分子内氢烷氧化/Claisen重排反应^★

Brønsted Acid-Catalyzed Intramolecular Hydroalkoxylation/Claisen Rearrangement of Ynamides^★