Synthesis of α-Sulfonyl Ketones via I2/TBHP Promoted Radical Sulfonylation of Silyl Enol Ethers with Sulfohydrazides under Mild Conditions †

doi:10.7503/cjcu20190424

Abstract

Abstract:

A I₂/TBHP mediated reaction of readily prepared silyl enol ethers with sulfonylhydrazides was developed for the synthesis of α-sulfonyl ketones under mild conditions. Twenty-two α-sulfonyl ketone derivatives were obtained in 22%—72% yields under the optimized reaction conditions. Their structures were confirmed by nuclear magnetic resonance spectroscopy(NMR). Moreover, the present catalytic protocol exhibited good functional group tolerance and substrate applicability, and various substituents such as halogen, nitro, trifluoromethyl, furan and naphthalene can be successfully converted to corresponding α-sulfonyl ketones. The preliminary mechanistic studies disclose that the reaction may proceed via a radical pathway.

Key words: α-Sulfonyl ketone;, Silyl enol ether, Sulfonylhydrazide, Radical reaction

CLC Number:

O626

TrendMD:

TANG Yucai,QU Huang,ZHANG Wenxi,WANG Feifei,WANG Gang. Synthesis of α-Sulfonyl Ketones via I₂/TBHP Promoted Radical Sulfonylation of Silyl Enol Ethers with Sulfohydrazides under Mild Conditions ^†[J]. Chem. J. Chinese Universities, 2020, 41(1): 118.

Figures/Tables 7

References 27

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Compd.	Appearance	Yield(%)	Melting point/℃	Compd.	Appearance	Yield(%)	Melting point/℃
3a	White solid	66	99—101	3m	White solid	32	99—100
3b	White solid	52	107—108	3n	White solid	25	106—107
3c	White solid	55	123—124	3o	White solid	22	79—80
3d	White solid	49	132—133	3p	White solid	58	80—81
3e	White solid	50	122—123	3q	White solid	59	92—93
3f	White solid	50	144—145	3r	White solid	55	148—149
3g	Yellow solid	72	140—141	3s	White solid	45	130—131
3h	White solid	65	108—109	3t	White solid	39	116—117
3i	White solid	34	126—127	3u	White solid	63	106—107
3j	White solid	45	102—103	3v	Colorless oil	50
3l	White solid	40	139—140	3w	White solid	46	130—131

Compd.	Appearance	Yield(%)	Melting point/℃	Compd.	Appearance	Yield(%)	Melting point/℃
3a	White solid	66	99—101	3m	White solid	32	99—100
3b	White solid	52	107—108	3n	White solid	25	106—107
3c	White solid	55	123—124	3o	White solid	22	79—80
3d	White solid	49	132—133	3p	White solid	58	80—81
3e	White solid	50	122—123	3q	White solid	59	92—93
3f	White solid	50	144—145	3r	White solid	55	148—149
3g	Yellow solid	72	140—141	3s	White solid	45	130—131
3h	White solid	65	108—109	3t	White solid	39	116—117
3i	White solid	34	126—127	3u	White solid	63	106—107
3j	White solid	45	102—103	3v	Colorless oil	50
3l	White solid	40	139—140	3w	White solid	46	130—131

Compd.	¹H NMR(500 MHz), δ	¹³C NMR(125 MHz), δ
3a	7.97(d,J=7.4 Hz, 2H), 7.77(d, J=8.2 Hz, 2H), 7.62(t, J=7.4 Hz, 1H), 7.46(t, J=7.8 Hz, 2H), 7.33(d, J=8.2 Hz, 2H), 4.72(s, 2H), 2.44(s, 3H)	188.2, 145.4, 135.8, 135.8, 134.3, 129.8, 129.3, 128.8, 128.6, 63.6, 21.6
3b	7.86(d,J=8.3 Hz, 2H), 7.75(d, J=8.3 Hz, 2H), 7.33(d, J=8.0 Hz, 2H), 7.27(d, J=9.4 Hz, 2H), 4.69(s, 2H), 2.44(s, 3H), 2.42(s, 3H)	187.6, 145.6, 145.3, 135.9, 133.4, 129.8, 129.5, 129.5, 128.6, 63.6, 21.8, 21.6
3c	8.03—7.98(m, 2H), 7.75(d, J=8.3 Hz, 2H), 7.34(d, J=8.1 Hz, 2H), 7.19—7.13(m, 2H), 4.69(s, 2H), 2.45(s, 3H)	186.6, 166.5(d, J=256.3 Hz ), 145.5, 135.7, 132.2(d, J=2.5 Hz ), 132.2, 129.9, 128.6, 116.1(d, J=22.5 Hz ), 63.8, 21.6
3d	7.90(d,J=8.6 Hz, 2H), 7.74(d, J=8.2 Hz, 2H), 7.45(d, J=8.6 Hz, 2H), 7.34(d, J=8.1 Hz, 2H), 4.69(s, 2H), 2.44(s, 3H)	187.0, 145.5, 141.0, 135.7, 134.1, 130.8, 129.9, 129.2, 128.5, 63.7, 21.6
3e	7.84—7.81(m, 2H), 7.76—7.71(m, 2H), 7.66—7.61(m, 2H), 7.35(d, J=7.9 Hz, 2H), 4.67(s, 2H), 2.46(s, 3H)	187.3, 145.6, 134.6, 132.6, 132.3, 130.9, 129.9, 129.0, 128.6, 63.8, 21.8
3f	8.07(d, J=8.2 Hz, 2H), 7.74(d, J=8.2 Hz, 4H), 7.34(d, J=8.0 Hz, 2H), 4.75(s, 2H), 2.45(s, 3H)	187.5, 145.7, 138.4, 135.6, 135.4(q,J=32.5 Hz), 129.9, 129.8, 128.6, 125.9(q, J=3.8 Hz), 123.4(q, J=271.3 Hz), 63.9, 21.6
3g	8.34(d, J=8.8 Hz, 2H), 8.16(d, J=8.8 Hz, 2H), 7.75(d, J=8.3 Hz, 2H), 7.37(d, J=8.1 Hz, 2H), 4.75(s, 2H), 2.47(s, 3H)	186.9, 150.9, 145.9, 139.9, 135.4, 130.5, 130.0, 128.5, 123.9, 64.2, 21.6
3h	7.77—7.74(m, 2H), 7.74—7.68(m, 2H), 7.40(d, J=7.6 Hz, 1H), 7.33(dd, J=17.5, 7.8 Hz, 3H), 4.71(s, 2H), 2.42(s, 3H), 2.37(s, 3H)	188.3, 145.3, 138.7, 135.8, 135.8, 135.1, 129.8, 129.6, 128.7, 128.6, 126.6, 63.5, 21.7, 21.3
3i	8.01(t,J=1.8 Hz, 1H), 7.89(dt, J=7.8, 1.3 Hz, 1H), 7.77—7.71(m, 3H), 7.40—7.32(m, 3H), 4.68(s, 2H), 2.45(s, 3H)	186.9, 145.6, 137.4, 137.1, 135.6, 132.1, 130.4, 129.9, 128.6, 127.9, 123.2, 63.7, 21.6
3j	7.75(dd, J=12.7, 8.4 Hz, 3H), 7.42(td, J=7.5, 1.1 Hz, 1H), 7.32(d, J=8.0 Hz, 2H), 7.30—7.23(m, 2H), 4.69(s, 2H), 2.44(s, 3H), 2.43(s, 3H)	190.6, 145.2, 140.0, 136.1, 135.8, 132.7, 132.3, 130.4, 129.8, 128.5, 125.9, 65.6, 21.7, 21.5
3l	8.42(s, 1H), 8.00—7.90(m, 2H), 7.91—7.83(m, 2H), 7.77(d, J=8.2 Hz, 2H), 7.67—7.51(m, 2H), 7.28(d, J=7.9 Hz, 2H), 4.84(s, 2H), 2.38(s, 3H)	188.0, 145.4, 135.9, 135.7, 133.1, 132.2, 132.1, 129.9, 129.8, 129.3, 128.8, 128.6, 127.8, 127.1, 123.9, 63.7, 21.6
3m	7.82(dd,J=3.9, 1.0 Hz, 1H), 7.79—7.73(m, 3H), 7.34(d, J=8.0 Hz, 2H), 7.17(dd, J=4.9, 3.9 Hz, 1H), 4.61(s, 2H), 2.44(s, 3H)	180.3, 145.5, 143.3, 136.3, 135.2, 129.9, 129.7, 128.7, 128.6, 64.8, 21.6
3n	7.79—7.74(m, 2H), 7.61(dd, J=1.6, 0.7 Hz, 1H), 7.36—7.31(m, 3H), 6.58(dd, J=3.7, 1.7 Hz, 1H), 4.57(s, 2H), 2.44(s, 3H)	175.9, 151.9, 148.1, 145.4, 135.7, 129.8, 128.5, 120.4, 113.2, 63.6, 21.7
3o	8.01—7.96(m, 2H), 7.66(d, J=8.3 Hz, 2H), 7.63—7.57(m, 1H), 7.52—7.45(m, 2H), 7.31(d, J=8.0 Hz, 2H), 5.16(q, J=6.9 Hz, 1H), 2.43(s, 3H), 1.56(d, J=6.9 Hz, 3H)	192.6, 145.3, 136.3, 133.9, 129.8, 129.5, 129.2, 128.7, 125.5, 65.0, 21.7, 13.2
3p	7.94(ddd, J=17.6, 8.4, 1.1 Hz, 4H), 7.64(dt, J=22.5, 7.4 Hz, 2H), 7.54(t, J=7.8 Hz, 2H), 7.47(t, J=7.8 Hz, 2H), 4.75(s, 2H)	187.9, 138.8, 135.7, 134.4, 134.2, 129.3, 129.2, 128.9, 128.6, 63.4
3q	7.96(dd, J=8.4, 1.1 Hz, 2H), 7.83—7.78(m, 2H), 7.65—7.59(m, 1H), 7.51—7.46(m, 2H), 7.01—6.96(m, 2H), 4.71(s, 2H), 3.88(s, 3H)	187.8, 163.7, 135.4, 133.9, 130.5, 129.8, 128.98, 128.5, 114.1, 63.6, 55.6
3r	8.00—7.87(m, 4H), 7.63(t, J=6.8 Hz, 1H), 7.49(q, J=6.7 Hz, 2H), 7.21(t, J=7.7 Hz, 2H), 4.75(s, 2H)	187.7, 165.5(d, J=256 Hz), 135.4, 134.3, 134.3, 131.7(d, J=10 Hz), 129.0, 128.7, 116.3(d, J=23 Hz), 63.3
3s	7.94(dt, J=8.5, 1.5 Hz, 2H), 7.86—7.81(m, 2H), 7.67—7.61(m, 1H), 7.55—7.47(m, 4H), 4.75(s, 2H)	187.9, 141.2, 137.1, 135.6, 134.5, 130.2, 129.5, 129.2, 128.9, 63.3
3t	7.95(d, J=7.4 Hz, 2H), 7.75(d, J=8.6 Hz, 2H), 7.68(d, J=8.5 Hz, 2H), 7.63(t, J=7.4 Hz, 1H), 7.48(t, J=7.8 Hz, 2H), 4.75(s, 2H)	187.9, 137.8, 135.6, 134.5, 132.5, 130.2, 129.7, 129.2, 128.9, 63.3
3u	8.06(d, J=8.2 Hz, 2H), 7.92(dd, J=8.3, 1.1 Hz, 2H), 7.81(d, J=8.3 Hz, 2H), 7.67—7.61(m, 1H), 7.49(t, J=7.9 Hz, 2H), 4.80(s, 2H)	187.5, 141.8, 135.7, 135.3(d,J=15.7 Hz), 134.4, 129.2, 129.0, 128.8, 126.9(q, J=3 Hz), 123.1(q, J=272 Hz), 62.9
3v	8.08—8.02(m, 1H), 7.97—7.91(m, 2H), 7.64—7.55(m, 3H), 7.51—7.41(m, 3H), 5.06(s, 2H)	187.6, 136.2, 135.5, 134.9, 134.3, 132.5, 131.8, 131.6, 128.9, 128.7, 127.3, 60.9
3w	8.48(s, 1H), 8.01—7.91(m, 5H), 7.87(dd, J=8.6, 1.9 Hz, 1H), 7.73—7.65(m, 1H), 7.65—7.55(m, 2H), 7.45(t, J=7.8 Hz, 2H), 4.81(s, 2H)	187.9, 135.5, 135.4, 135.3, 134.1, 131.8, 130.4, 129.4, 129.3, 129.1, 128.6,128.0, 127.8, 127.5, 122.7, 63.6

Compd.	¹H NMR(500 MHz), δ	¹³C NMR(125 MHz), δ
3a	7.97(d,J=7.4 Hz, 2H), 7.77(d, J=8.2 Hz, 2H), 7.62(t, J=7.4 Hz, 1H), 7.46(t, J=7.8 Hz, 2H), 7.33(d, J=8.2 Hz, 2H), 4.72(s, 2H), 2.44(s, 3H)	188.2, 145.4, 135.8, 135.8, 134.3, 129.8, 129.3, 128.8, 128.6, 63.6, 21.6
3b	7.86(d,J=8.3 Hz, 2H), 7.75(d, J=8.3 Hz, 2H), 7.33(d, J=8.0 Hz, 2H), 7.27(d, J=9.4 Hz, 2H), 4.69(s, 2H), 2.44(s, 3H), 2.42(s, 3H)	187.6, 145.6, 145.3, 135.9, 133.4, 129.8, 129.5, 129.5, 128.6, 63.6, 21.8, 21.6
3c	8.03—7.98(m, 2H), 7.75(d, J=8.3 Hz, 2H), 7.34(d, J=8.1 Hz, 2H), 7.19—7.13(m, 2H), 4.69(s, 2H), 2.45(s, 3H)	186.6, 166.5(d, J=256.3 Hz ), 145.5, 135.7, 132.2(d, J=2.5 Hz ), 132.2, 129.9, 128.6, 116.1(d, J=22.5 Hz ), 63.8, 21.6
3d	7.90(d,J=8.6 Hz, 2H), 7.74(d, J=8.2 Hz, 2H), 7.45(d, J=8.6 Hz, 2H), 7.34(d, J=8.1 Hz, 2H), 4.69(s, 2H), 2.44(s, 3H)	187.0, 145.5, 141.0, 135.7, 134.1, 130.8, 129.9, 129.2, 128.5, 63.7, 21.6
3e	7.84—7.81(m, 2H), 7.76—7.71(m, 2H), 7.66—7.61(m, 2H), 7.35(d, J=7.9 Hz, 2H), 4.67(s, 2H), 2.46(s, 3H)	187.3, 145.6, 134.6, 132.6, 132.3, 130.9, 129.9, 129.0, 128.6, 63.8, 21.8
3f	8.07(d, J=8.2 Hz, 2H), 7.74(d, J=8.2 Hz, 4H), 7.34(d, J=8.0 Hz, 2H), 4.75(s, 2H), 2.45(s, 3H)	187.5, 145.7, 138.4, 135.6, 135.4(q,J=32.5 Hz), 129.9, 129.8, 128.6, 125.9(q, J=3.8 Hz), 123.4(q, J=271.3 Hz), 63.9, 21.6
3g	8.34(d, J=8.8 Hz, 2H), 8.16(d, J=8.8 Hz, 2H), 7.75(d, J=8.3 Hz, 2H), 7.37(d, J=8.1 Hz, 2H), 4.75(s, 2H), 2.47(s, 3H)	186.9, 150.9, 145.9, 139.9, 135.4, 130.5, 130.0, 128.5, 123.9, 64.2, 21.6
3h	7.77—7.74(m, 2H), 7.74—7.68(m, 2H), 7.40(d, J=7.6 Hz, 1H), 7.33(dd, J=17.5, 7.8 Hz, 3H), 4.71(s, 2H), 2.42(s, 3H), 2.37(s, 3H)	188.3, 145.3, 138.7, 135.8, 135.8, 135.1, 129.8, 129.6, 128.7, 128.6, 126.6, 63.5, 21.7, 21.3
3i	8.01(t,J=1.8 Hz, 1H), 7.89(dt, J=7.8, 1.3 Hz, 1H), 7.77—7.71(m, 3H), 7.40—7.32(m, 3H), 4.68(s, 2H), 2.45(s, 3H)	186.9, 145.6, 137.4, 137.1, 135.6, 132.1, 130.4, 129.9, 128.6, 127.9, 123.2, 63.7, 21.6
3j	7.75(dd, J=12.7, 8.4 Hz, 3H), 7.42(td, J=7.5, 1.1 Hz, 1H), 7.32(d, J=8.0 Hz, 2H), 7.30—7.23(m, 2H), 4.69(s, 2H), 2.44(s, 3H), 2.43(s, 3H)	190.6, 145.2, 140.0, 136.1, 135.8, 132.7, 132.3, 130.4, 129.8, 128.5, 125.9, 65.6, 21.7, 21.5
3l	8.42(s, 1H), 8.00—7.90(m, 2H), 7.91—7.83(m, 2H), 7.77(d, J=8.2 Hz, 2H), 7.67—7.51(m, 2H), 7.28(d, J=7.9 Hz, 2H), 4.84(s, 2H), 2.38(s, 3H)	188.0, 145.4, 135.9, 135.7, 133.1, 132.2, 132.1, 129.9, 129.8, 129.3, 128.8, 128.6, 127.8, 127.1, 123.9, 63.7, 21.6
3m	7.82(dd,J=3.9, 1.0 Hz, 1H), 7.79—7.73(m, 3H), 7.34(d, J=8.0 Hz, 2H), 7.17(dd, J=4.9, 3.9 Hz, 1H), 4.61(s, 2H), 2.44(s, 3H)	180.3, 145.5, 143.3, 136.3, 135.2, 129.9, 129.7, 128.7, 128.6, 64.8, 21.6
3n	7.79—7.74(m, 2H), 7.61(dd, J=1.6, 0.7 Hz, 1H), 7.36—7.31(m, 3H), 6.58(dd, J=3.7, 1.7 Hz, 1H), 4.57(s, 2H), 2.44(s, 3H)	175.9, 151.9, 148.1, 145.4, 135.7, 129.8, 128.5, 120.4, 113.2, 63.6, 21.7
3o	8.01—7.96(m, 2H), 7.66(d, J=8.3 Hz, 2H), 7.63—7.57(m, 1H), 7.52—7.45(m, 2H), 7.31(d, J=8.0 Hz, 2H), 5.16(q, J=6.9 Hz, 1H), 2.43(s, 3H), 1.56(d, J=6.9 Hz, 3H)	192.6, 145.3, 136.3, 133.9, 129.8, 129.5, 129.2, 128.7, 125.5, 65.0, 21.7, 13.2
3p	7.94(ddd, J=17.6, 8.4, 1.1 Hz, 4H), 7.64(dt, J=22.5, 7.4 Hz, 2H), 7.54(t, J=7.8 Hz, 2H), 7.47(t, J=7.8 Hz, 2H), 4.75(s, 2H)	187.9, 138.8, 135.7, 134.4, 134.2, 129.3, 129.2, 128.9, 128.6, 63.4
3q	7.96(dd, J=8.4, 1.1 Hz, 2H), 7.83—7.78(m, 2H), 7.65—7.59(m, 1H), 7.51—7.46(m, 2H), 7.01—6.96(m, 2H), 4.71(s, 2H), 3.88(s, 3H)	187.8, 163.7, 135.4, 133.9, 130.5, 129.8, 128.98, 128.5, 114.1, 63.6, 55.6
3r	8.00—7.87(m, 4H), 7.63(t, J=6.8 Hz, 1H), 7.49(q, J=6.7 Hz, 2H), 7.21(t, J=7.7 Hz, 2H), 4.75(s, 2H)	187.7, 165.5(d, J=256 Hz), 135.4, 134.3, 134.3, 131.7(d, J=10 Hz), 129.0, 128.7, 116.3(d, J=23 Hz), 63.3
3s	7.94(dt, J=8.5, 1.5 Hz, 2H), 7.86—7.81(m, 2H), 7.67—7.61(m, 1H), 7.55—7.47(m, 4H), 4.75(s, 2H)	187.9, 141.2, 137.1, 135.6, 134.5, 130.2, 129.5, 129.2, 128.9, 63.3
3t	7.95(d, J=7.4 Hz, 2H), 7.75(d, J=8.6 Hz, 2H), 7.68(d, J=8.5 Hz, 2H), 7.63(t, J=7.4 Hz, 1H), 7.48(t, J=7.8 Hz, 2H), 4.75(s, 2H)	187.9, 137.8, 135.6, 134.5, 132.5, 130.2, 129.7, 129.2, 128.9, 63.3
3u	8.06(d, J=8.2 Hz, 2H), 7.92(dd, J=8.3, 1.1 Hz, 2H), 7.81(d, J=8.3 Hz, 2H), 7.67—7.61(m, 1H), 7.49(t, J=7.9 Hz, 2H), 4.80(s, 2H)	187.5, 141.8, 135.7, 135.3(d,J=15.7 Hz), 134.4, 129.2, 129.0, 128.8, 126.9(q, J=3 Hz), 123.1(q, J=272 Hz), 62.9
3v	8.08—8.02(m, 1H), 7.97—7.91(m, 2H), 7.64—7.55(m, 3H), 7.51—7.41(m, 3H), 5.06(s, 2H)	187.6, 136.2, 135.5, 134.9, 134.3, 132.5, 131.8, 131.6, 128.9, 128.7, 127.3, 60.9
3w	8.48(s, 1H), 8.01—7.91(m, 5H), 7.87(dd, J=8.6, 1.9 Hz, 1H), 7.73—7.65(m, 1H), 7.65—7.55(m, 2H), 7.45(t, J=7.8 Hz, 2H), 4.81(s, 2H)	187.9, 135.5, 135.4, 135.3, 134.1, 131.8, 130.4, 129.4, 129.3, 129.1, 128.6,128.0, 127.8, 127.5, 122.7, 63.6

Entry	Catalyst	Oxidant	Solvent	Yield^b(%)	Entry	Catalyst	Oxidant	Solvent	Yield^b(%)
1	KI	TBHP	CH₃CN	25	10	I₂	TBHP	DCE	66
2	I₂	TBHP	CH₃CN	43	11	I₂	TBHP	Toluene	Trace
3	NaI	TBHP	CH₃CN	20	12		I₂O₅	DCE	Trace
4	TBAI	TBHP	CH₃CN	32	13	I₂	K₂S₂O₈	DCE	Trace
5	I₂	TBHP	CH₃CN	55^c	14	I₂	DTBP	DCE	Trace
6	I₂	TBHP	CH₃CN	34^d	15	I₂	TBHP	DCE	44
7	I₂	TBHP	THF	Trace	16	I₂	TBHP	DCE	64^e
8	I₂	TBHP	1,4-Dioxane	35	17	I₂	TBHP	DCE	62^f
9	I₂	TBHP	DMF	Trace

Synthesis of α-Sulfonyl Ketones via I₂/TBHP Promoted Radical Sulfonylation of Silyl Enol Ethers with Sulfohydrazides under Mild Conditions ^†

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