α-芳基-α-羟基酮(酯)与全氟烷基磺酰氟/甲基三乙氧基硅烷/碱体系不期望的氧化反应

doi:10.7503/cjcu20150276

高等学校化学学报 ›› 2015, Vol. 36 ›› Issue (12): 2441.doi: 10.7503/cjcu20150276

α-芳基-α-羟基酮(酯)与全氟烷基磺酰氟/甲基三乙氧基硅烷/碱体系不期望的氧化反应

严兆华¹(), 赵冬冬¹, 胡伟¹, 田欢¹, 李小松¹, 田伟生²()

1. 南昌大学化学学院, 南昌 330031
2. 中国科学院上海有机化学研究所, 上海 200032

收稿日期:2015-04-08 出版日期:2015-12-10 发布日期:2015-10-13
作者简介:联系人简介: 严兆华, 男, 博士, 教授, 主要从事新型有机方法学和有机合成方面的研究. E-mail:yanzh@ncu.edu.cn;田伟生, 男, 博士, 研究员, 博士生导师, 主要从事有机合成特别是资源化学和甾体化学领域的反应和合成研究. E-mail:wstian@sioc.ac.cn
基金资助:
国家自然科学基金(批准号: 21362022)资助

Unexpected Oxidation of α-Aryl-α-hydroxyketone(ester) with Perfluoroalkanosulfonyl Fluoride/Methyltriethoxysilane/Base System^†

YAN Zhaohua^1,^*(), ZHAO Dongdong¹, HU Wei¹, TIAN Huan¹, LI Xiaosong¹, TIAN Weisheng^2,^*()

1. College of Chemistry, Nanchang University, Nanchang 330031, China
2. Shanghai Institute of Organic Chenistry, Chinese Academy of Sciences, Shanghai 200032, China

Received:2015-04-08 Online:2015-12-10 Published:2015-10-13
Contact: YAN Zhaohua,TIAN Weisheng E-mail:yanzh@ncu.edu.cn;wstian@sioc.ac.cn
Supported by:
† Supported by the National Natural Science Foundation of China(No.21362022)

摘要/Abstract

摘要：

研究了全氟烷基磺酰氟/甲基三乙氧基硅烷/碱体系与α-芳基-α-羟基酮(酯)化合物不期望的氧化反应, 以中等到优良的收率生成了相应的1,2-二酮(α-酮酸酯)产物. 所用全氟烷基磺酰氟为全氟正丁基磺酰氟或全氟正辛基磺酰氟; 碱为1,8-二氮杂二环[5.4.0]十一碳-7-烯(DBU). 提出了一种可能的反应机理. 为制备芳基取代的1,2-二酮(或α-酮酸酯)化合物提供了一种新方法.

关键词: α-芳基-α-羟基酮(酯), 全氟烷基磺酰氟, 甲基三乙氧基硅烷, 芳基取代的1,2-二酮(α-酮酸酯)

Abstract:

Aryl substituted 1,2-diketone(α-ketonic esters) have been widely used as important intermediates for syntheses of ligands, bioactive molecules and functional materials. As a class of excellent hydroxyl-activating reagent, the application of perfluoroalkanosulfonyl fluoride in organic synthesis has been intensively investigated in the past decades. In this work, oxidation of α-aryl-α-hydroxyketone(ester) with perfluoroalkanosulfonyl fluoride/methyltriethoxysilane/base system in CH₂Cl₂ at room temperature was further studied and the corresponding 1,2-diketone(ketonic ester) was generated in moderate to good yields. Perfluoroalkanosulfonyl fluoride used is n-perfluorobutanosulfonyl fluoride or n-perfluorooctanosulfonyl fluoride; base used is 1,8-diazabicyclo[5.4.0]undec-7-ene(DBU). A reasonable reaction mechanism was proposed to explain the results. A novel method for the preparation of aryl substituted 1,2-diketone(ketonic ester) was developed. The application scope of perfluoroalkanosulfonyl fluoride in organic synthesis was broadened.

Key words: α-Aryl-α-hydroxyketone(ester), Perfluoroalkanosulfonyl fluoride, Methyltriethoxysilane, Aryl substituted 1,2-diketone(α-ketonic ester)

中图分类号:

O626

TrendMD:

严兆华, 赵冬冬, 胡伟, 田欢, 李小松, 田伟生. α-芳基-α-羟基酮(酯)与全氟烷基磺酰氟/甲基三乙氧基硅烷/碱体系不期望的氧化反应. 高等学校化学学报, 2015, 36(12): 2441.

YAN Zhaohua, ZHAO Dongdong, HU Wei, TIAN Huan, LI Xiaosong, TIAN Weisheng. Unexpected Oxidation of α-Aryl-α-hydroxyketone(ester) with Perfluoroalkanosulfonyl Fluoride/Methyltriethoxysilane/Base System^†. Chem. J. Chinese Universities, 2015, 36(12): 2441.

图/表 5

参考文献 28

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Compd.	Appearance	Yield(%)	m.p./℃	HRMS(ESI)[M+Na]⁺(calcd.), m/z
2a	Pale yellow liquid	64	—	201.0536(201.0543)
2b	Pale yellow liquid	70	—	187.0627(187.0619)
2d	Pale yellow solid	97	97—98	246.1296(246.1282)
2e'	Pale yellow solid	96	107—108	261.2557(261.2555)
2f	Pale yellow liquid	94	—	215.1770(215.1773)
2g	Pale yellow solid	92	90—91(93—94^[27])
2h	Pale yellow solid	96	161—163(161—162^[28])

Compd.	Appearance	Yield(%)	m.p./℃	HRMS(ESI)[M+Na]⁺(calcd.), m/z
2a	Pale yellow liquid	64	—	201.0536(201.0543)
2b	Pale yellow liquid	70	—	187.0627(187.0619)
2d	Pale yellow solid	97	97—98	246.1296(246.1282)
2e'	Pale yellow solid	96	107—108	261.2557(261.2555)
2f	Pale yellow liquid	94	—	215.1770(215.1773)
2g	Pale yellow solid	92	90—91(93—94^[27])
2h	Pale yellow solid	96	161—163(161—162^[28])

Entry	Substrate	Product	Yield^b(%)	Entry	Substrate	Product	Yield^b(%)
1	1a	2a	64	6	1e	2e'	93
2^c	1b	2b	70	7	1f	2f	92
3	1b	2a	62	8	1g	2g	98
4	1c	2a	56	9	1h	2h	96
5^d	1d	2d	97

Entry	Substrate	Product	Yield^b(%)	Entry	Substrate	Product	Yield^b(%)
1	1a	2a	64	6	1e	2e'	93
2^c	1b	2b	70	7	1f	2f	92
3	1b	2a	62	8	1g	2g	98
4	1c	2a	56	9	1h	2h	96
5^d	1d	2d	97

α-芳基-α-羟基酮(酯)与全氟烷基磺酰氟/甲基三乙氧基硅烷/碱体系不期望的氧化反应

Unexpected Oxidation of α-Aryl-α-hydroxyketone(ester) with Perfluoroalkanosulfonyl Fluoride/Methyltriethoxysilane/Base System^†

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Entry	Solvent	Base	Yield^b(%)	Entry	Solvent	Base	Yield^b(%)
1	CH₂Cl₂	DBU	64	6	CH₂Cl₂	Et₃N	36
2	THF	DBU	57	7	CH₂Cl₂	Pyridine	18
3	MeCN	DBU	60	8^c	CH₂Cl₂	DBU	62
4	PhCH₃	DBU	53	9^d	CH₂Cl₂	DBU	30
5	CH₃COCH₃	DBU	61	10^e	CH₂Cl₂	DBU	0

Entry	Substrate	Product	Yield^b(%)	Entry	Substrate	Product	Yield^b(%)
1	1a	2a	64	6	1e	2e'	93
2^c	1b	2b	70	7	1f	2f	92
3	1b	2a	62	8	1g	2g	98
4	1c	2a	56	9	1h	2h	96
5^d	1d	2d	97

Entry	Substrate	Product	Yield^b(%)	Entry	Substrate	Product	Yield^b(%)
1	1a	2a	64	6	1e	2e'	93
2^c	1b	2b	70	7	1f	2f	92
3	1b	2a	62	8	1g	2g	98
4	1c	2a	56	9	1h	2h	96
5^d	1d	2d	97

Entry	Substrate	Product	Yield^b(%)	Entry	Substrate	Product	Yield^b(%)
1	1a	2a	64	6	1e	2e'	93
2^c	1b	2b	70	7	1f	2f	92
3	1b	2a	62	8	1g	2g	98
4	1c	2a	56	9	1h	2h	96
5^d	1d	2d	97

Entry	Substrate	Product	Yield^b(%)	Entry	Substrate	Product	Yield^b(%)
1	1a	2a	64	6	1e	2e'	93
2^c	1b	2b	70	7	1f	2f	92
3	1b	2a	62	8	1g	2g	98
4	1c	2a	56	9	1h	2h	96
5^d	1d	2d	97

α-芳基-α-羟基酮(酯)与全氟烷基磺酰氟/甲基三乙氧基硅烷/碱体系不期望的氧化反应

Unexpected Oxidation of α-Aryl-α-hydroxyketone(ester) with Perfluoroalkanosulfonyl Fluoride/Methyltriethoxysilane/Base System†

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Unexpected Oxidation of α-Aryl-α-hydroxyketone(ester) with Perfluoroalkanosulfonyl Fluoride/Methyltriethoxysilane/Base System^†

Entry	Substrate	Product	Yield^b(%)	Entry	Substrate	Product	Yield^b(%)
1	1a	2a	64	6	1e	2e'	93
2^c	1b	2b	70	7	1f	2f	92
3	1b	2a	62	8	1g	2g	98
4	1c	2a	56	9	1h	2h	96
5^d	1d	2d	97

Entry	Substrate	Product	Yield^b(%)	Entry	Substrate	Product	Yield^b(%)
1	1a	2a	64	6	1e	2e'	93
2^c	1b	2b	70	7	1f	2f	92
3	1b	2a	62	8	1g	2g	98
4	1c	2a	56	9	1h	2h	96
5^d	1d	2d	97