Difluoromethylation of Dicyanoalkylidenes by Electrophilic S-（Difluoromethyl）sulfonium Salt： Efficient Construction of Difluoromethylated All-carbon-substituted Centers†

doi:10.7503/cjcu20200383

Abstract

Abstract:

An efficient approach for difluoromethylation of dicyanoalkylidenes by electrophilic S-（difluoromethyl）sulfonium salt under organic base was described. A wide range of structurally and functionally diverse dicyanoalkylidenes was readily transferred into corresponding desirable difluoromethylated compounds bearing difluoromethylated all-carbon-substituted centers in good to excellent yields under standard reaction conditions.

Key words: S-（Difluoromethyl）sulfonium salt, Difluoromethylation, All-carbon-substituted centers, 1, 1-Dicyanoalkylidene

CLC Number:

O621.3

TrendMD:

QIN Wenbing, LIN Weifeng, LI Xin, XIONG Wei, LIU Guokai. Difluoromethylation of Dicyanoalkylidenes by Electrophilic S-（Difluoromethyl）sulfonium Salt： Efficient Construction of Difluoromethylated All-carbon-substituted Centers^†[J]. Chem. J. Chinese Universities, 2020, 41(10): 2230.

Figures/Tables 6

References 30

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Compd.	Appearance	m.p./℃(ref.)	MS^a(calcd.), m/z
2a	White solid	115.1—117.5(115.3—117.8)^[25]	194(194)
2b	Yellow solid	—	225.0(225.1)
2c	Light yellow solid	—	225.0(225.1)
2d	White solid	—	225.0(225.1)
2e	Brown solid	—	255.0(255.1)
2f	White solid	—	272.9(273.0), 275.0(275.0)^b
2g	White solid	—	208(208)
2h	Off?white solid	171.9—173.8(172.9—174.0)^[28]	208(208)
2i	Colorless oil	—	146(146)
2j	Yellow solid	121.0—123.0(120.9—123.2)^[25]	274(274), 276(276)^b
2k	Yellow solid	122.6—125.1(122.2—125.6)^[25]	212(212)
2m	White solid	157.1—159.5(157.2—159.3)^[25]	180(180)
2n	White solid	70.2—71.9(70.2—71.9)^[25]	194(194)
2o	White solid	—	194(194)
4a	White solid	—	168(168)
4b	Light yellow solid	93.2—94.(93.5—94.5)^[27]	246(246), 248(248)^b
4c	White solid	113.2—115.1(113—115)^[26]	260(260), 262(262)^b
4d	White solid	—	196(196)
4e	White solid	—	210(210)
4f	White solid	84.5—86.8(85.4—88.9)^[25]	244(244)
4g	Yellow solid	130.2—131.9(130—132)^[29]	268(268)
4h	Light yellow solid	114.0—116.3(114.1—116.1)^[25]	218(218)
4i	White solid	86.8—88.3(87—88)^[27]	174(174)
4j	Colorless oil	—	182(182)

Compd.	Appearance	m.p./℃(ref.)	MS^a(calcd.), m/z
2a	White solid	115.1—117.5(115.3—117.8)^[25]	194(194)
2b	Yellow solid	—	225.0(225.1)
2c	Light yellow solid	—	225.0(225.1)
2d	White solid	—	225.0(225.1)
2e	Brown solid	—	255.0(255.1)
2f	White solid	—	272.9(273.0), 275.0(275.0)^b
2g	White solid	—	208(208)
2h	Off?white solid	171.9—173.8(172.9—174.0)^[28]	208(208)
2i	Colorless oil	—	146(146)
2j	Yellow solid	121.0—123.0(120.9—123.2)^[25]	274(274), 276(276)^b
2k	Yellow solid	122.6—125.1(122.2—125.6)^[25]	212(212)
2m	White solid	157.1—159.5(157.2—159.3)^[25]	180(180)
2n	White solid	70.2—71.9(70.2—71.9)^[25]	194(194)
2o	White solid	—	194(194)
4a	White solid	—	168(168)
4b	Light yellow solid	93.2—94.(93.5—94.5)^[27]	246(246), 248(248)^b
4c	White solid	113.2—115.1(113—115)^[26]	260(260), 262(262)^b
4d	White solid	—	196(196)
4e	White solid	—	210(210)
4f	White solid	84.5—86.8(85.4—88.9)^[25]	244(244)
4g	Yellow solid	130.2—131.9(130—132)^[29]	268(268)
4h	Light yellow solid	114.0—116.3(114.1—116.1)^[25]	218(218)
4i	White solid	86.8—88.3(87—88)^[27]	174(174)
4j	Colorless oil	—	182(182)

Compd.	Appearance	m.p./℃	HRMS(calcd.)^a, m/z
3a	White solid	95.0—97.1	277.1148(277.1147)
3b	White solid	59.5—62.0	275.0987(275.0990)
3c	White solid	47.0—49.1	275.0987(275.0990)
3d	White solid	79.0—81.2	307.1248(307.1253)
3e	White solid	124.2—126.3	305.1098(305.1096)
3f	White solid	110.2—112.4	355.0246(355.0252)
3g	White solid	84.0—85.6	291.1308(291.1303)
3h	White solid	66.1—67.8	291.1306(291.1303)
3i	Colorless oil	—	229.1147(229.1147)
3j	White solid	135.0—137.2	357.0044(357.0045)
3k	Light yellow solid	97.1—99.8	295.0714(295.0711)
3l	Light yellow solid	144.7—146.8	313.0614(313.0617)
3m	White solid	85.7—88.0	263.0987(263.0990)
3n	White solid	100.7—102.4	277.1144(277.1147)
3o	White solid	76.5—78.6	277.1145(277.1147)
5a	White solid	37.3—39.0	251.0987(251.0990)
5b	White solid	53.0—55.1	329.0096(329.0096)
5c	White solid	91.7—94.0	343.0246(343.0252)
5d	Colorless oil	—	279.1315(279.1303)
5e	Colorless oil	—	293.1458(293.1460)
5f	White solid	81.3—82.4	327.1300(327.1303)
5g	White solid	115.3—117.2	351.1301(351.1303)
5h	White solid	86.8—88.0	301.1144(301.1147)
5i	Colorless oil	—	257.0551(257.0555)
5j	White solid	37.0—39.3	265.1148(265.1147)

Compd.	Appearance	m.p./℃	HRMS(calcd.)^a, m/z
3a	White solid	95.0—97.1	277.1148(277.1147)
3b	White solid	59.5—62.0	275.0987(275.0990)
3c	White solid	47.0—49.1	275.0987(275.0990)
3d	White solid	79.0—81.2	307.1248(307.1253)
3e	White solid	124.2—126.3	305.1098(305.1096)
3f	White solid	110.2—112.4	355.0246(355.0252)
3g	White solid	84.0—85.6	291.1308(291.1303)
3h	White solid	66.1—67.8	291.1306(291.1303)
3i	Colorless oil	—	229.1147(229.1147)
3j	White solid	135.0—137.2	357.0044(357.0045)
3k	Light yellow solid	97.1—99.8	295.0714(295.0711)
3l	Light yellow solid	144.7—146.8	313.0614(313.0617)
3m	White solid	85.7—88.0	263.0987(263.0990)
3n	White solid	100.7—102.4	277.1144(277.1147)
3o	White solid	76.5—78.6	277.1145(277.1147)
5a	White solid	37.3—39.0	251.0987(251.0990)
5b	White solid	53.0—55.1	329.0096(329.0096)
5c	White solid	91.7—94.0	343.0246(343.0252)
5d	Colorless oil	—	279.1315(279.1303)
5e	Colorless oil	—	293.1458(293.1460)
5f	White solid	81.3—82.4	327.1300(327.1303)
5g	White solid	115.3—117.2	351.1301(351.1303)
5h	White solid	86.8—88.0	301.1144(301.1147)
5i	Colorless oil	—	257.0551(257.0555)
5j	White solid	37.0—39.3	265.1148(265.1147)

Compd.	¹H NMR(500 MH_Z, CDCl₃), δ	¹³C NMR(126 MH_Z, CDCl₃), δ	¹⁹F NMR(471 MH_Z, CDCl₃), δ
3a	7.57—7.52(m, 1H), 7.32—7.26(m, 3H), 6.86(t, J=4.9 Hz, 1H), 6.39(t, J=54.3 Hz, 1H), 2.84—2.77(m, 2H), 2.51—2.44(m, 2H)	137.2, 136.5, 129.1, 129.0, 128.5, 127.0, 123.2, 122.5, 110.1(t, J=3.0 Hz), 109.9(t, J=259.3 Hz),46.8(t, J=24.7 Hz), 27.3, 23.5	-119.1(d, J=54.4 Hz)
3b	7.26(t, J=8.1 Hz, 1H), 7.18(d, J=7.9 Hz, 1H), 6.92(d, J=8.2 Hz, 1H), 6.86(t, J=4.9 Hz, 1H), 6.40(t, J=54.4 Hz, 1H), 3.86(s, 3H), 2.79(t, J=8.2 Hz, 2H), 2.41(td, J=8.2, 5.0 Hz, 2H)	156.8, 136.7, 129.4, 127.2, 125.5, 123.1, 115.0, 111.6, 110.2(t, J=2.8 Hz), 109.9(d, J=259.1 Hz), 55.7, 47.1(t, J=24.8 Hz), 23.0, 18.9	-119.3(d, J=54.5 Hz)
Compd.	¹H NMR(500 MH_Z, CDCl₃), δ	¹³C NMR(126 MH_Z, CDCl₃), δ	¹⁹F NMR(471 MH_Z, CDCl₃), δ
3c	7.50(d, J=8.3 Hz, 1H), 6.82(d, J=8.1 Hz, 2H), 6.73(t, J=4.9 Hz, 1H), 6.39(t, J=54.3 Hz, 1H), 3.85(s, 3H), 2.79(t, J=8.0 Hz, 2H), 2.46(td, J=8.0, 4.9 Hz, 2H)	159.8, 139.4, 133.5, 123.9, 122.9, 121.4, 115.3, 111.3, 110.2(t, J=2.9 Hz), 109.9(t, J=259.3 Hz), 55.4, 46.8(t, J=24.7 Hz), 27.9, 23.4	-118.6(d, J=53.9 Hz)
3d	7.18(d, J=8.3 Hz, 1H), 7.13(d, J=1.7 Hz, 1H), 6.87(t, J=4.8 Hz, 1H), 6.83(dd, J=8.3, 2.1 Hz, 1H), 6.40(t, J=54.3 Hz, 1H), 3.82(s, 3H), 2.72(t, J=7.9 Hz, 2H), 2.47—2.41(m, 2H)	158.5, 137.3, 129.7, 129.4, 129.1, 123.2, 113.5, 110.2(t, J=2.7 Hz), 110.0(t, J=259.4 Hz), 109.9, 55.6, 47.0(t, J=24.7 Hz), 26.5, 24.0	-119.1(d, J=54.3 Hz)
3e	7.15(s, 1H), 6.77(s, 1H), 6.71(t, J=4.9 Hz, 1H), 6.32(t, J=54.3 Hz, 1H), 3.91(s, 3H), 3.89(s, 3H), 2.72(t, J=8.1 Hz, 2H), 2.43(td, J=8.1, 7.7, 5.0 Hz, 2H)	149.2, 147.4, 133.8, 130.6, 122.9, 120.9, 112.1, 110.3(t, J=259.8 Hz), 110.2(t, J=2.8 Hz), 107.2, 56.3, 56.0, 46.7(t, J=24.7 Hz), 27.1, 23.6	-118.6(d, J=54.4 Hz)
3f	7.65(s, 1H), 7.43(dd, J=8.0, 1.7 Hz, 1H), 7.14(d, J=8.0 Hz, 1H), 6.92(t, J=4.9 Hz, 1H), 6.35(t, J=54.1 Hz, 1H), 2.75(t, J=8.0 Hz, 2H), 2.47(td, J=8.0, 5.0 Hz, 2H)	138.2, 136.2, 132.1, 130.6, 130.5, 125.8, 122.6, 120.6, 109.9(t, J=259.8 Hz), 109.9(d, J=4.7 Hz), 26.9, 23.5	-118.8(d, J=54.1 Hz)
3g	7.57(d, J=7.5 Hz, 1H), 7.37—7.27(m, 3H), 6.82—6.74(m, 1H), 6.41(t, J=54.3 Hz, 1H), 3.00—2.92(m, 1H), 2.61(ddd, J=17.3, 6.6, 4.2 Hz, 1H), 2.32(dt, J=17.2, 6.1 Hz, 1H), 1.21(d, J=7.0 Hz, 3H)	142.2, 135.0, 129.5, 127.8, 127.6, 126.8, 122.6, 122.5, 110.1(dd, J=51.3, 4.3 Hz), 109.8(t, J=259.2 Hz), 46.8(t, J=24.8 Hz), 31.5, 31.0, 19.5	-118.2(d, J=54.1 Hz), -118.8(d, J=54.6 Hz), -118.9(d, J=54.4 Hz), -119.5(d, J=54.0 Hz)
3h	7.67(dd, J=5.6, 3.5 Hz, 1H), 7.35(dt, J=7.4, 3.7 Hz, 2H), 7.32—7.28(m, 1H), 7.00(t, J=7.6 Hz, 1H), 5.87(t, J=54.1 Hz, 1H), 2.53(t, J=7.1 Hz, 2H), 2.15(p, J=7.1 Hz, 2H), 1.98(q, J=7.3 Hz, 2H)	141.9, 138.6, 132.8, 129.9, 129.6, 127.1, 126.4, 125.2, 110.9(t, J=258.9 Hz), 110.3(t, J=3.0 Hz),47.7(t, J=24.9 Hz), 33.6, 31.4, 24.7	-120.8(d, J=53.9 Hz)
3i	6.41(s, 1H), 5.94(t, J=54.4 Hz, 1H), 2.22(qd, J=8.5, 7.4, 3.2 Hz, 4H), 1.80—1.73(m, 2H), 1.69—1.62(m, 2H)	134.5, 123.2, 111.2(t, J=260.1 Hz), 109.7(t, J=3.1 Hz), 48.7(t, J=24.2 Hz), 25.7, 25.5, 22.2, 20.9	-118.8(d, J=54.3 Hz)
3j	7.62(d, J=2.1 Hz, 1H), 7.42(dd, J=8.7, 2.2 Hz, 1H), 6.88(d, J=8.6 Hz, 1H), 6.59(t, J=4.1 Hz, 1H), 6.34(t, J=54.0 Hz, 1H), 4.89(d, J=4.1 Hz, 2H)	153.7, 134.3, 129.4, 125.6, 120.2, 119.5, 119.2, 114.2, 109.61(t, J=260.6 Hz), 108.97(t, J=2.9 Hz), 64.6, 45.71(t, J=25.7 Hz)	-117.7(d, J=54.0 Hz)
3k	7.73—7.69(m, 1H), 7.52—7.46(m, 1H), 7.30—7.25(m, 2H), 6.87(t, J=6.1 Hz, 1H), 6.24(t, J=54.1 Hz, 1H), 3.39(d, J=6.1 Hz, 2H)	135.8, 129.9, 129.5, 129.12, 128.4, 126.3, 124.8, 124.5, 110.1(t, J=260.1 Hz), 109.9(t, J=2.9 Hz), 47.1(t, J=25.2 Hz), 24.9	-118.4(d, J=54.0 Hz)
3l	7.52—7.44(m, 2H), 7.04(td, J=8.3, 2.5 Hz, 1H), 6.94(t, J=6.1 Hz, 1H), 6.23(t, J=54.1 Hz, 1H), 3.38(d, J=6.1 Hz, 2H)	160.8(d, J=247.0 Hz), 131.6, 130.9(d, J=3.3 Hz), 130.6(d, J=7.9 Hz), 129.8(d, J=7.4 Hz), 124.6, 117.0(d, J=21.8 Hz), 112.3(d, J=24.9 Hz), 110.2(t, J=260.5 Hz), 109.7(t, J=2.9 Hz), 108.1, 47.1(t, J=25.5 Hz), 25.1	-113.1(m, F), -118.5(d, J=54.1 Hz, 2F)
3m	7.69(d, J=7.6 Hz, 1H), 7.60(d, J=7.3 Hz, 1H), 7.44(t, J=7.3 Hz, 1H), 7.42—7.38(m, 1H), 7.13(t, J=2.1 Hz, 1H), 6.31(t, J=54.2 Hz, 1H), 3.65—3.59(m, 2H)	144.2, 139.1, 138.2, 128.3, 127.1, 126.9, 124.8, 120.0, 110.5(t, J=260.7 Hz), 109.2(t, J=3.0 Hz), 43.1(t, J=25.8 Hz), 38.3	-117.8(d, J=54.1 Hz)
3n	7.46—7.41(m, 2H), 7.18(d, J=7.8 Hz, 1H), 7.07(t, J=1.9 Hz, 1H), 6.29(t, J=54.2 Hz, 1H), 3.53(s, 2H), 2.45(s, 3H).	141.4, 139.4, 138.6, 137.1, 128.2, 128.0, 124.6, 120.6, 110.5(t, J=260.6 Hz), 109.4(t, J=2.7 Hz), 43.3(t, J=25.9 Hz), 38.1, 21.8	-118.0(d, J=54.2 Hz)
Compd.	¹H NMR(500 MH_Z, CDCl₃), δ	¹³C NMR(126 MH_Z, CDCl₃), δ	¹⁹F NMR(471 MH_Z, CDCl₃), δ
3o	7.68(d, J=7.8 Hz, 1H), 7.45(d, J=7.4 Hz, 1H), 7.34(t, J=7.6 Hz, 1H), 7.26(t, J=7.8 Hz, 1H), 6.23(t, J=54.4 Hz, 1H), 3.54(s, 2H), 2.47(s, 3H)	150.5, 140.8, 140.7, 126.9, 125.8, 123.9, 119.2, 118.1, 110.6(t, J=260.4 Hz), 109.7(t, J=3.2 Hz), 45.6, 41.7(t, J=26.1 Hz), 15.3	-118.9(d, J=54.4 Hz)
5a	7.49—7.42(m, 3H), 7.41—7.37(m, 2H), 6.14(s, 1H), 5.86(t, J=53.9 Hz, 1H), 5.73(s, 1H)	134.9, 134.4, 130.0, 129.2, 128.7, 125.4, 110.5(t, J=259.2 Hz), 109.5(t, J=2.9 Hz),48.2(t, J=25.1 Hz)	-120.4(d, J=54.3 Hz)
5b	7.59(d, J=8.4 Hz, 2H), 7.27(d, J=8.3 Hz, 2H), 6.15(s, 1H), 5.87(t, J=53.9 Hz, 1H), 5.75(s, 1H)	134.0, 133.2, 132.4, 130.3, 126.0, 124.6, 110.5(t, J=259.6 Hz), 109.3(t, J=2.9 Hz), 48.0(t, J=25.3 Hz)	-120.5(d, J=53.8 Hz)
5c	7.66—7.60(m, 2H), 7.17—7.10(m, 2H), 6.65(q, J=6.8 Hz, 1H), 5.78(t, J=53.9 Hz, 1H), 1.63(d, J=6.8 Hz, 3H)	136.2, 132.8, 131.6, 131.0, 125.7, 124.2, 110.6(t, J=258.8 Hz), 109.5(t, J=2.9 Hz), 48.9(t, J=25.0 Hz), 15.3	-120.8(d, J=53.8 Hz)
5d	7.46(dd, J=5.1, 1.9 Hz, 3H), 7.23(dd, J=6.6, 2.8 Hz, 2H), 6.52(t, J=7.4 Hz, 1H), 5.76(t, J=54.0 Hz, 1H), 1.93(p, J=7.5 Hz, 2H), 0.99(t, J=7.5 Hz, 3H)	141.9, 132.2, 129.9, 129.6, 129.4, 125.5, 110.6(t, J=258.4 Hz), 109.7(t, J=2.8 Hz), 49.2(t, J=24.9 Hz), 22.9, 13.2	-121.7(d, J=53.8 Hz)
5e	7.48—7.44(m, 3H), 7.23(dd, J=6.6, 2.9 Hz, 2H), 6.30(d, J=10.1 Hz, 1H), 5.75(t, J=54.0 Hz, 1H), 2.15(dp, J=10.1, 6.6 Hz, 1H), 0.97(d, J=6.6 Hz, 6H)	146.9, 132.3, 129.8, 129.6, 129.3, 123.9, 110.6(t, J=258.4 Hz), 109.7(t, J=2.9 Hz), 49.2(t, J=24.8 Hz), 29.0, 22.0, 21.7	-121.8(d, J=54.0 Hz)
5f	7.57—7.50(m, 3H), 7.40—7.33(m, 3H), 7.26(t, J=7.3 Hz, 1H), 7.19(t, J=7.6 Hz, 2H), 6.97(d, J=7.6 Hz, 2H), 5.89(t, J=53.9 Hz, 1H)	137.3, 133.2, 132.7, 130.1, 130.1, 130.0, 129.8, 129.3, 128.5, 125.4, 110.8(t, J=258.9 Hz),109.7(t, J=2.8 Hz), 50.2(t, J=25.0 Hz)	-121.5(d, J=54.0 Hz)
5g	8.76(s, 1H), 8.69(d, J=8.2 Hz, 1H), 7.99(d, J=8.2 Hz, 1H), 7.96(d, J=7.8 Hz, 1H), 7.87(d, J=8.8 Hz, 1H), 7.79(d, J=8.8 Hz, 1H), 7.74(t, J=7.6 Hz, 1H), 7.69(t, J=7.0 Hz, 1H), 7.63(dd, J=8.2, 1.5 Hz, 2H), 6.31(s, 1H), 5.95(t, J=53.8 Hz, 1H), 5.92(s, 1H)	135.2, 132.6, 132.4, 132.3, 130.3, 129.8, 129.6, 128.9, 128.8, 127.5, 127.3, 126.3, 126.1, 125.8, 123.3, 122.6, 110.7(t, J=259.3 Hz), 109.7(t, J=2.9 Hz), 48.5(t, J=25.1 Hz)	-120.8(d, J=53.8 Hz)
5h	7.91(d, J=8.5 Hz, 1H), 7.90—7.87(m, 3H), 7.61—7.54(m, 2H), 7.47(dd, J=8.4, 1.9 Hz, 1H), 6.22(d, J=1.0 Hz, 1H), 5.90(t, J=53.9 Hz, 1H), 5.83(s, 1H)	135.0, 133.5, 132.9, 131.7, 129.2, 128.5, 128.4, 127.8, 127.6, 127.3, 125.7, 125.5, 110.6(t, J=259.3 Hz), 109.6(t, J=2.9 Hz), 48.3(t, J=25.2 Hz)	-120.8(d, J=53.9 Hz)
5i	7.43—7.39(m, 1H), 7.35(d, J=3.6 Hz, 1H), 7.10(dd, J=5.2, 3.7 Hz, 1H), 6.09(s, 1H), 6.08(t, J=54.2 Hz, 1H), 5.95(d, J=1.5 Hz, 1H)	135.0, 128.2, 128.0, 127.9, 127.8, 124.9, 110.4(t, J=260.0 Hz), 109.4(t, J=2.9 Hz), 48.1(d, J=25.3 Hz)	-119.5(d, J=54.5 Hz)
5j	7.47—7.33(m, 5H), 6.17(t, J=54.2 Hz, 1H), 5.67—5.53(m, 1H), 2.47(d, J=1.4 Hz, 3H)	150.9, 140.6, 129.4, 128.8, 126.1, 111.3(t, J=259.1 Hz), 109.7(t, J=3.1 Hz), 109.2(t, J=2.7 Hz), 40.1(t, J=25.1 Hz), 18.5	-120.5(d, J=54.0 Hz)