Metal-Free Imination of Sulfides and Sulfoxides
FULL PAPER
1
Compound 2q: Colorless oil; H NMR (400 MHz, CDCl3): d=3.42–3.31
analysis calcd (%) for C11H14F3NO3S2: C 40.11, H 4.28, N 4.25; found: C
39.99, H 4.21, N 4.20.
(m, 2H), 3.28–3.19 (m, 2H), 2.65–2.50 (m, 2H), 2.25–2.10 ppm (m, 2H);
13C NMR (75 MHz, CDCl3): d=120.3 (q,
JACTHNGUTERNNU(G C,F)=323 Hz), 52.4,
Compound 3h: Colorless needles (recrystallized from dichloromethane/
hexane); m.p. 50–518C; 1H NMR (400 MHz, CDCl3): d=8.01 (d, J=
7.8 Hz, 2H), 7.78 (t, J=7.2 Hz, 1H), 7.67 (dd, J=7.8, 7.2 Hz, 2H), 6.85
(dd, J=16.2, 9.4 Hz, 1H), 6.64 (d, J=16.2 Hz, 1H), 6.36 ppm (d, J=
9.4 Hz, 1H); 13C NMR (75 MHz, CDCl3): d=136.3, 136.2, 135.3, 131.1,
26.7 ppm; IR (neat): n˜ =2954, 2883, 1448, 1414, 1329, 1171, 997, 895, 768,
735, 609 cmÀ1; elemental analysis calcd (%) for C5H8F3NO2S2: C 25.53, H
3.43, N 5.95; found: C 25.52, H 3.44, N 6.25.
Compound 2s: Colorless plates (recrystallized from dichloromethane/
hexane); m.p. 84–888C; 1H NMR (400 MHz, CDCl3): d=4.52 (ddd, J=
13.2, 10.0, 2.0 Hz, 2H), 4.01 (dt, J=13.2, 3.8 Hz, 2H), 3.22 (ddd, J=14.0,
10.0, 3.8 Hz, 2H), 2.97 ppm (ddd, J=14.0, 3.8, 2.0 Hz, 2H); 13C NMR
130.2, 127.9, 119.2 ppm (q, JACTHUNRTGNEUNG(C,F)=321 Hz); IR (KBr): n˜ =3111, 3087,
3024, 2966, 1444, 1385, 1344, 1265, 1194, 1130, 1095, 1061, 997, 958, 798,
771, 742, 690, 640 cmÀ1; elemental analysis calcd (%) for C9H8F3NO3S2: C
36.12, H 2.69, N 4.68; found: C 35.86, H 2.76, N 4.89.
(75 MHz, CDCl3): d=120.2 (q,
JACTHNGUTER(NNUG C,F)=323 Hz), 59.4, 42.1 ppm; IR
(KBr): n˜ =3012, 2941, 2881, 1462, 1410, 1383, 1333, 1219, 1180, 1157,
1103, 1065, 1018, 991, 966, 833, 768, 741, 615 cmÀ1; elemental analysis
calcd (%) for C5H8F3NO3S2: C 23.90, H 3.21, N 5.57; found: C 23.77, H
3.14, N 5.62.
Compound 3i: White needles (recrystallized from ethyl acetate/hexane);
m.p. 58–598C; 1H NMR (400 MHz, CDCl3): d=3.86–3.74 (m, 2H), 3.50–
3.37 (m, 2H), 2.49–2.32 ppm (m, 4H); 13C NMR (75 MHz, CDCl3): d =
119.2 (q, JACTHNUTRGNE(NUG C,F)=321 Hz), 54.9, 23.3 ppm; IR (KBr): n˜ =3018, 2976, 2945,
1450, 1400, 1350, 1286, 1203, 1134, 1101, 1045, 903, 787, 750, 727, 656,
634 cmÀ1; elemental analysis calcd (%) for C5H8F3NO3S2: C 23.90, H
3.21, N 5.57; found: C 24.14, H 3.19, N 5.73.
Compound 2t: Colorless needles (recrystallized from dichloromethane/
hexane); m.p. 134–1358C; H NMR (400 MHz, CDCl3): d=4.29 (brd, J=
12.8 Hz, 1H), 4.10 (d, J=12.8 Hz, 1H), 3.61–3.53 (m, 1H), 3.20 (dt, J=
1
13.1, 2.6 Hz, 1H), 2.82–2.73 (m, 1H), 2.71–2.59 (m, 2H), 2.46–2.33 ppm
(m, 1H); 13C NMR (75 MHz, CDCl3): d=120.2 (q, J
ACHTNUTRGNE(NUG C,F)=323 Hz),
49.3, 49.2, 28.0, 27.7 ppm; IR (KBr): n˜ =2997, 2929, 1433, 1336, 1217,
1178, 1138, 1086, 999, 924, 891, 820, 771, 748, 727, 652, 613 cmÀ1; elemen-
tal analysis calcd (%) for C5H8F3NO2S3: C 22.47, H 3.02, N 5.24; found:
C 22.58, H 3.04, N 5.24.
Acknowledgements
We gratefully acknowledge the Ministry of Education, Culture, Sports,
Science, and Technology of Japan for financial support in the form of a
grant.
1
Compound 2u: Colorless oil; H NMR (400 MHz, [D6]acetone): d=3.72–
3.59 (m, 4H), 3.46–3.36 (m, 2H), 2.91–2.78 ppm (m, 2H); 13C NMR
(75 MHz, CDCl3): d=120.2 (q,
JACTHNGUTER(NNUG C,F)=322 Hz), 43.8, 19.1 ppm; IR
(neat): n˜ =2981, 2929, 1408, 1335, 1186, 1130, 1018, 945, 895, 771, 742,
609 cmÀ1; elemental analysis calcd (%) for C5H8F3NO2S3: C 22.47, H
3.02, N 5.24; found: C 22.23, H 3.06, N 5.01.
(Ed.: T. Wirth), Springer, Berlin, 2003; f) J. Du Bois, Chemtracts
2005, 18, 1–13; g) C. G. Espino, J. Du Bois in Modern Rhodium-
Catalyzed Organic Reactions (Ed.: P. A. Evans), Wiley-VCH, Wein-
heim, 2005, Chapter 17.
Compound cis-2v: Colorless prisms (recrystallized from acetone/
hexane); m.p. 1928C (decomposition); 1H NMR (400 MHz, [D6]DMSO):
d=4.04–3.91 (m, 4H), 3.84–3.71 ppm (m, 4H); 13C NMR (75 MHz,
[D6]acetone): d=121.2 (q, J
ACHTUNGTRENN(UNG C,F)=322 Hz), 40.3 ppm; IR (KBr): n˜ =
3010, 2931, 1417, 1336, 1225, 1182, 1157, 1136, 1039, 989, 908, 775, 746,
613 cmÀ1
; HRMS (ESI): m/z: calcd for C6H8F6N2NaO4S4: 436.9169
[M+Na]+; found: 436.9167.
Compound trans-2v: White powder (recrystallized from acetone); m.p.
254–2558C (decomposition); 1H NMR (400 MHz, [D6]DMSO): d=4.07
(d, J=11.5 Hz, 4H), 3.52 ppm (d, J=11.5 Hz, 4H); 13C NMR (75 MHz,
[D6]DMSO): d=119.8 (q, JACTHNUGRTENUNG(C,F)=323 Hz), 32.0 ppm; IR (KBr): n˜ =
2991, 2947, 1412, 1333, 1223, 1180, 1119, 1003, 899, 777, 750, 627 cmÀ1; el-
emental analysis calcd (%) for C6H8F6N2O4S4: C 17.39, H 1.95, N 6.76;
found: C 17.63, H 2.22, N 7.02.
Compounds (Ed.: K.-y. Akiba), Wiley-VCH, Weinheim, 1999, Chap-
ter 12.
Compound 2w: Colorless needles (recrystallized from dichloromethane/
hexane); m.p. 131–1328C; 1H NMR (400 MHz, CDCl3): d=8.04 (dd, J=
7.7, 1.3 Hz, 2H), 7.77 (dd, J=7.7, 1.3 Hz, 2H), 7.66 (dt, J=1.3, 7.7 Hz,
2H), 7.60 ppm (dt, J=1.3, 7.7 Hz, 2H); 13C NMR (75 MHz, CDCl3): d=
À
[4] For recent examples of C H insertion, see: a) M. R. Fructos, S. Tro-
46, 5184–5186; d) C. Liang, F. Collet, F. Robert-Peillard, P. Muller,
[5] For olefin aziridinations, see: a) K. Guthikonda, J. Du Bois, J. Am.
131.9, 131.3, 130.0, 129.4, 126.2, 120.3 ppm (q,
JACTHUNGTERNNU(G C,F)=323 Hz); IR
(KBr): n˜ =3078, 2999, 1572, 1450, 1338, 1217, 1165, 1132, 1043, 972, 752,
702, 611 cmÀ1; elemental analysis calcd (%) for C13H8F3NO2S3: C 42.97,
H 2.22, N 3.85; found: C 42.92, H 2.44, N 3.84.
Compound 3c: Colorless plates (recrystallized from diethyl ether/
hexane); m.p. 89–918C; 1H NMR (400 MHz, CDCl3): d=7.92 (d, J=
8.4 Hz, 2H), 7.48 (d, J=8.4 Hz, 2H), 3.49 (s, 3H), 2.51 ppm (s, 3H);
13C NMR (75 MHz, CDCl3): d=147.0, 134.1, 130.8, 127.4, 119.2 (q, J-
ACHTUNGTRENNUNG
741, 688, 627 cmÀ1
; HRMS (ESI): m/z: calcd for C9H10F3NNaO3S2:
[7] Sulfides and sulfoxides: a) O. G. Mancheno, J. Dallimore, A. Plant,
C. Bolm, Org. Lett. 2009, 11, 2429–2432; b) F. Collet, R. H. Dodd,
Bolm, Chem. Eur. J. 2007, 13, 6674–6681; d) O. G. Mancheno, C.
Bolm, Org. Lett. 2006, 8, 2349–2352; e) G. Y. Cho, C. Bolm, Org.
6, 1305–1307; g) D. Leca, A. Toussaint, C. Mareau, L. Fensterbank,
K. Song, M. Amatore, L. Fensterbank, E. Lacote, M. Malacria,
323.9952 [M+Na]+; found: 323.9952; elemental analysis calcd (%) for
C9H10F3NO3S2: C 35.88, H 3.35, N 4.65; found: C 35.71, H 3.53, N 4.65.
Compound 3 f: Colorless needles (recrystallized from dichloromethane/
hexane); m.p. 93–948C; 1H NMR (400 MHz, CDCl3): d=7.06 (s, 2H),
3.56 (s, 3H), 2.72 (s, 6H), 2.35 ppm (s, 3H); 13C NMR (75 MHz, CDCl3):
d=145.2, 139.7, 133.4, 131.3, 119.2 (q, JACTHNUTRGNEU(GN C,F)=321.4 Hz), 47.0, 22.8,
21.1 ppm; IR (KBr): n˜ =3022, 2978, 2941, 1603, 1560, 1456, 1385, 1344,
1263, 1186, 1138, 1066, 958, 860, 791, 766, 741, 706, 623 cmÀ1; elemental
Chem. Eur. J. 2010, 16, 8713 – 8718
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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