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

doi:10.7503/cjcu20150276

Abstract

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)

CLC Number:

O626

TrendMD:

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^†[J]. Chem. J. Chinese Universities, 2015, 36(12): 2441.

Figures/Tables 5

References 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