金催化选择性氧化共轭炔基炔酰胺合成4-羰基丁-2-炔酰胺

doi:10.6023/cjoc202007019

有机化学 ›› 2021, Vol. 41 ›› Issue (1): 376-383.DOI: 10.6023/cjoc202007019 上一篇下一篇

所属专题：热点论文虚拟合集

研究论文

金催化选择性氧化共轭炔基炔酰胺合成4-羰基丁-2-炔酰胺

万万^a, 刘继兵^a, 黄学良^a^,^*()

a 中国科学院福建物质结构研究所中国科学院大学煤制乙二醇及相关技术中科院重点实验室福州 350002

收稿日期:2020-07-06 修回日期:2020-08-04 发布日期:2020-08-19
通讯作者: 黄学良
作者简介:
* Corresponding author. E-mail: huangxl@fjirsm.ac.cn
基金资助:
国家自然科学基金(21871259); 国家自然科学基金(2191244); 中国科学院战略性先导科技专项B类(XDB20000000)

Gold-Catalyzed Selective Oxidation of 1,3-Diynamides to Access 4-Oxo-but-2-ynamides

Wan Wan^a, Jibing Liu^a, Xueliang Huang^a^,^*()

a Laboratory of Coal to Ethylene Glycol and Its Related Technology, Fujian Institute of Research on the Structure of Matter, University of Chinese Academy of Sciences, Fuzhou 350002

Received:2020-07-06 Revised:2020-08-04 Published:2020-08-19
Contact: Xueliang Huang
Supported by:
the National Natural Science Foundation of China(21871259); the National Natural Science Foundation of China(2191244); the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB20000000)

文章分享

1. cjoc202007019辅助材料.pdf(6658KB)

摘要/Abstract

通过金催化选择性氧化1,3-共轭炔基炔酰胺, 为4-羰基丁-2-炔酰胺化合物的合成提供了一种新的方法. 这种含有活化的不饱和炔烃的1,4-双羰基化合物是有机化学中一种重要的合成子. 利用该金催化氧化方法, 可以高度选择性地对共轭炔烃的1,4-位进行氧化得到2-炔-4-羰基丁酰胺化合物, 而不是生成较为常见的1,2-双羰基化合物. 在该选择性氧化的条件下, 可以以较高的收率得到一系列4-羰基丁-2-炔酰胺化合物.

关键词: 共轭炔酰胺, 金催化, 选择性氧化, 双羰基化合物

A gold-catalyzed selective oxidation of 1,3-diynamides has been developed to provide a novel approach to 4-oxo-but-2-ynamides. The products possess activated C—C triple bond, and often serve as versatile building blocks in synthetic community. This gold-catalyzed selective oxidation of 1,3-diynamides to provide 4-oxo-but-2-ynamides is noteworthy, since the traditional 1,2-dicarbonyl type products were not observed. Under standard conditions, a range of 4-oxo-but-2-yna- mide derivatives were obtained in moderate to high yields.

Key words: 3-diynamides, gold catalysis, selective oxidation, dicarbonyl compounds

引用此文

万万, 刘继兵, 黄学良. 金催化选择性氧化共轭炔基炔酰胺合成4-羰基丁-2-炔酰胺[J]. 有机化学, 2021, 41(1): 376-383.

Wan Wan, Jibing Liu, Xueliang Huang. Gold-Catalyzed Selective Oxidation of 1,3-Diynamides to Access 4-Oxo-but-2-ynamides[J]. Chinese Journal of Organic Chemistry, 2021, 41(1): 376-383.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 6

Scheme 1. Generation ofα-carbonyl gold carbene through oxidative addition of alkynes

Entry	Variation from standard condition	Time/h	Yield ^b /%
1	—	1.5	85
2	Oxidant (R=H)	10	trace
3	Oxidant (R=Br)	6	63
4	Oxidant (R=Me)	7	trace
5	Quinoline- N-oxide as oxidant	5	19
6	DMSO as oxidant	22	21
7	Diphenyl sulfoxide as oxidant	22	72
8	JohnphosAuNTf ₂as catalyst	2	19
9	JohnphosAuOMs as catalyst	9	46
10	BrettphosAu(MeCN)SbF ₆ as catalyst	2	78
11	^t BuXphosAu(MeCN)SbF ₆ as catalyst	8	55
12	Cu(OTf) ₂ as catalyst	5.5	40
13	Zn(OTf) ₂ as catalyst	6	8
14	AgOTf as catalyst	3	30
15	DCE as solvent	2	73
16	THF as solvent	15	32
17	React at 30 ℃	9	85
18	React at 60 ℃	2	85

Table 1. Reaction condition studies

Scheme 2. Gold-catalyzed selective oxidative reaction of 1,3-diynamides

. a Standard conditions: diynamides1 (0.15 mmol), gold-catalyst (5 mol%), 2-chloropyridine-N-oxide (2.5 equiv.), DCM (1.5 mL), stirred under an atmosphere of argon at 50 ℃ for 2 h;b Reaction time: 5 h;c Reaction time: 7 h;d Reaction time: 12 h. Substrate scope

Scheme 3.

Figure 1. Crystal struture of 2l Thermal ellipsoids are drawn at 50% probability. Hydrogen atoms were omitted for clarity, CCDC: 2012393

Scheme 4. Plausible reaction mechanism

参考文献 10

[1]	(a) Doyle M.P.; Forbes D.C. Chem. Rev. 1998, 98, 911.
	(b) Davies H.M.; Manning J.R. Nature 2008, 451, 417.
	(c) Zhang Z.; Zhang Y.; Wang J. ACS Catal. 2011, 1, 1621.
	(d) Zhu S.F.; Zhou Q.L. Acc. Chem. Res. 2012, 45, 1365.
	(e) Liu Z.; Wang J. J. Org. Chem. 2013, 78, 10024.
	(f) Jia M.; Ma S. Angew. Chem., Int. Ed. 2016, 55, 9134.
	(g) Xia Y.; Qiu D.; Wang J. Chem. Rev. 2017, 117, 13810.
	(h) Zhu D.; Chen L.; Fan H.; Yao Q.; Zhu S. Chem. Soc. Rev. 2020, 49, 908.
	(i) Zhang H.M.; Li L.Z.; Shen F.Q.; Cai T.; Shen R.P. Chin. J. Org. Chem. 2020, 40, 873. (in Chinese)
	( 张慧苗, 李灵芝, 沈方旗, 蔡涛, 沈润溥, 有机化学, 2020, 49, 873.).
[2]	(a) Ye T.; McKervey M.A. Chem. Rev. 1994, 94, 1091.
	(b) Zhang Z.H.; Wang J.B. Tetrahedron 2008, 64, 6577.
	(c) Zhang Y.; Wang J. Chem. Commun. 2009, 5350.
	(d) Doyle M.P.; Duffy R.; Ratnikov M.; Zhou L. Chem. Rev. 2010, 110, 704.
	(e) Xiao Q.; Zhang Y.; Wang J. Acc. Chem. Res. 2013, 46, 236.
	(f) Ford A.; Miel H.; Ring A.; Slattery C.N.; Maguire A.R.; McKervey M.A. Chem. Rev. 2015, 115, 9981.
	(g) Gao Y.; Wang J.B. Chin. J. Org. Chem. 2018, 38, 1275. (in Chinese)
	( 郜云鹏, 王建波, 有机化学, 2018, 38, 1275.).
[3]	(a) Xiao J.; Li X. Angew. Chem., Int. Ed. 2011, 50, 7226.
	(b) Zhang L. Acc. Chem. Res. 2014, 47, 877.
	(c) Yeom H.S.; Shin S. Acc. Chem. Res. 2014, 47, 966.
	(d) Liu L.; Zhang J. Chem. Soc. Rev. 2016, 45, 506.
	(e) Zheng Z.; Wang Z.; Wang Y.; Zhang L. Chem. Soc. Rev. 2016, 45, 4448.
[4]	(a) Zificsak C.A.; Mulder J.A.; Hsung R.P.; Rameshkumar C.; Wei L.-L. Tetrahedron 2001, 57, 7575.
	(b) DeKorver K.A.; Li H.; Lohse A.G.; Hayashi R.; Lu Z.; Zhang Y.; Hsung R.P. Chem. Rev. 2010, 110, 5064.
	(c) Evano G.; Coste A.; Jouvin K. Angew. Chem., Int. Ed. 2010, 49, 2840.
	Evano G.; Jouvin K.; Coste A. Synthesis 2012, 45, 17.
	(e) Wang X.-N.; Yeom H.-S.; Fang L.-C.; He S.; Ma Z.-X.; Kedrowski B.L.; Hsung R.P. Acc. Chem. Res. 2014, 47, 560.
	(f) Evano G.; Theunissen C.; Lecomte M. Aldrichim. Acta 2015, 48, 59.
	(g) Pan F.; Shu C.; Ye L.-W. Org. Biomol. Chem. 2016, 14, 9456.
[5]	(a) Zhu L.; Yu Y.; Mao Z.; Huang X. Org. Lett. 2015, 17, 30.
	(b) Wu Y.; Zhu L.; Yu Y.; Luo X.; Huang X. J. Org. Chem. 2015, 80, 11407.
	(c) Yu Y.; Chen G.; Zhu L.; Liao Y.; Wu Y.; Huang X. J. Org. Chem. 2016, 81, 8142.
	(d) Cheng X.; Zhu L.; Lin M.; Chen J.; Huang X. Chem. Commun. 2017, 53, 3745.
	(e) Liao Y.; Zhu L.; Yu Y.H.; Chen G.; Huang X.L. Chin. J. Org. Chem. 2017, 37, 2785. (in Chinese)
	( 廖云, 朱磊, 俞颖华, 陈贵, 黄学良, 有机化学, 2017, 37, 2785.).
	(f) Lin M.; Zhu L.; Xia J.; Yu Y.; Chen J.; Mao Z.; Huang X. Adv. Synth. Catal. 2018, 360, 2280.
	(g) Liu J.; Chakraborty P.; Zhang H.; Zhong L.; Wang Z.; Huang X. ACS Catal. 2019, 9, 2610.
	(h) Zhu B.; Zhu L.; Xia J.; Huang S.; Huang X. Tetrahedron 2020, 131056.
[6]	Liu J.; Zhu L.; Wan W.; Huang X., Org. Lett. 2020, 22, 3279.
[7]	During the preparation of this work, a related work was published online: Skaria, M.; Hsu, Y. C.; Jiang, Y. T.; Lu, M. Y.; Kuo, T. C.; Cheng, M. J.; Liu, R. S.Org. Lett. 2020, 22, 4478.
[8]	(a) Xu C.F.; Xu M.; Jia Y.X.; Li C.Y. Org. Lett. 2011, 13, 1556.
	(b) Pan F.; Li X.-L.; Chen X.-M.; Shu C.; Ruan P.-P.; Shen C.-H.; Lu X.; Ye L.-W. ACS Catal. 2016, 6, 6055.
	(c) Shu C.; Shi C.Y.; Sun Q.; Zhou B.; Li T.Y.; He Q.; Lu X.; Liu R.S.; Ye L.W. ACS Catal. 2019, 9, 1019.
[9]	Shibata T.; Fujiwara D.; Endo K. Org. Biomol. Chem. 2008, 6, 464.
[10]	(a) Hamada T.; Ye X.; Stahl S.S. J. Am. Chem. Soc. 2008, 130, 833.
	(b) Coste A.; Karthikeyan G.; Couty F.; Evano G. Angew. Chem., Int. Ed. 2009, 48, 4381.
	(c) Yao B.; Liang Z.; Niu T.; Zhang Y. J. Org. Chem. 2009, 74, 4630.
	(d) Tu Y.; Zeng X.; Wang H.; Zhao J. Org. Lett. 2018, 20, 280.

[1]	崔效源, 周锋, 吴海虹, 周剑. 手性胺/金(I)协同催化的不对称串联反应研究[J]. 有机化学, 2022, 42(10): 3033-3050.
[2]	郑康河, 周丙伟, 金红卫, 刘运奎. 双官能膦配体-金(I)高效催化合成1,5-苯并二氮（艹卓）[J]. 有机化学, 2020, 40(8): 2520-2525.
[3]	麻鸿鹏, 白朝鲁门, 包永胜. 纳米金催化(杂环)芳基酯与卤代烷经由C—O键活化的酯交换反应[J]. 有机化学, 2019, 39(3): 734-746.
[4]	胡传峰, 周建豪, 黄志达, 傅惠惠, 彭新华. 金属钼酸类催化剂在双氧水作氧化剂下选择性氧化烯烃和醇[J]. 有机化学, 2018, 38(2): 486-491.
[5]	胡辉, 胡晓苹, 陈铭, 孙宁, 刘元红. 金催化的扩环反应:2,3-苯并二氮杂(艹卓)类化合物的高效合成[J]. 有机化学, 2018, 38(1): 190-199.
[6]	张小祥, 吕昌, 李萍, 雍万雄, 李静, 朱新宝. 金催化2-炔基芳基叠氮氧化重排一锅法快速合成苯并噁嗪-4-酮[J]. 有机化学, 2018, 38(1): 208-214.
[7]	廖云, 朱磊, 俞颖华, 陈贵, 黄学良. 金催化分子间炔烃的氮烯转移反应合成含氮杂环化合物[J]. 有机化学, 2017, 37(11): 2785-2799.
[8]	陈斌, 于丛军, 张国柱. 一种构建多取代吡唑的新策略[J]. 有机化学, 2015, 35(3): 625-632.
[9]	李龙, 周波, 叶龙武. 金催化分子间氧化炔酰胺合成α-氨基酰胺[J]. 有机化学, 2015, 35(3): 655-661.
[10]	黎龙香, 谢龙勇, 王风君, 何卫民, 向建南. 17-(2',5'-二取代噁唑基)-雄甾-4,16-二烯-3-酮的合成及抗肿瘤活性研究[J]. 有机化学, 2014, 34(9): 1864-1869.
[11]	鄢东, 吴超, 易卫国. 金催化炔烃与1,4-二氧六环的开环加成反应研究[J]. 有机化学, 2014, 34(9): 1857-1863.
[12]	王小勇, 李治章. 金催化氧化末端炔烃合成α-乙酰氧基甲基酮方法研究[J]. 有机化学, 2014, 34(3): 566-571.
[13]	刘开建, 刘宏伟, 王文革, 欧丽娟, 王津津, 胡波年. 金催化炔基膦酸酯水合反应合成β-羰基膦酸酯[J]. 有机化学, 2014, 34(10): 2007-2014.
[14]	张艳, 朱成建. Bu₄NAuCl₄催化的H₂O₂氧化的sp³-C—H键与sp³-C—H键的交叉偶联反应[J]. 有机化学, 2012, 32(11): 2090-2094.
[15]	杨为准, 李荣耀, 韩伟, 张卫东, 孙建松. 天然山奈酚5 位鼠李糖糖苷的高效合成[J]. 有机化学, 2012, 32(06): 1067-1071.

金催化选择性氧化共轭炔基炔酰胺合成4-羰基丁-2-炔酰胺

Gold-Catalyzed Selective Oxidation of 1,3-Diynamides to Access 4-Oxo-but-2-ynamides

RichHTML

PDF

补充材料

可视化

摘要/Abstract

引用此文

分享此文

图/表 6

参考文献 10

相关文章 15

编辑推荐

相关统计

本文评价