Full Paper
doi.org/10.1002/ejoc.202000198
EurJOC
European Journal of Organic Chemistry
2
3
3
3J3-Hax,4-H ≈ 13.3 Hz, 2 H, 3-Hax, 5-Hax), 2.38 (s, 3 H, Ar-Me), 2.63
(broad ddd, J3-Hax,3-Heq ≈ J3-Hax,2-Hax ≈ J3-Hax,4-H ≈ 13.2 Hz, 2 H, 3-
2
(broad ddd, 2J2-Hax,2-Heq ≈ 3J2-Hax,3-Hax ≈ 13.7 Hz, 3J2-Hax,3-Heq = 2.8 Hz,
Hax, 5-Hax), 2.18 (broad d, J3-Heq,3-Hax = 14.5 Hz, 2 H, 3-Heq, 5-Heq),
2
2
3
2 H, 2-Hax, 6-Hax), 2.97 (broad d, J2-Heq,2-Hax ≈ 14.8 Hz, 2 H, 2-Heq
,
2.39 (s, 3 H, Ar-Me), 3.00 (ddd, J2-Hax,2-Heq ≈ J2-Hax,3-Hax ≈ 13.5 Hz,
3
3
2
6-Heq), 7.22 (broad d, J = 7.2 Hz, 2 H, Ar-H), 7.78 (d, J = 8.3 Hz, 2
H, Ar-H); 13C NMR (125 MHz, CDCl3): δ = 17.9 (C-3, C-5), 21.6 (Ar-
CH3), 27.3 [C(CH3)3], 33.1 [C(CH3)3], 43.4 (C-2, C-6), 46.3 (C-4), 126.4
3J2-Hax,3-Heq = 2.9 Hz, 2 H, 2-Hax, 6-Hax), 3.88 (broad d, J2-Heq,2-Hax
≈
3
3
13.6 Hz, 2 H, 2-Heq, 6-Heq), 7.26 (d, J = 8.1, 2 H, Ar-H), 7.85 (d, J =
8.3, 2 H, Ar-H); 13C NMR (100 MHz, CDCl3): δ = 21.6 (Ar-CH3), 25.8
(Ar-CH), 129.4 (Ar-CH), 141.7 (Ar-C), 141.8 (Ar-C); IR (ATR): ν (cm–1) = (C-3, C-5), 27.6 [C(CH3)3], 32.7 [C(CH3)3], 45.9 (C-4), 53.0 (C-2, C-6),
˜
2954, 1597, 1467, 1426, 1366, 1272, 1134, 1090, 1020, 1008, 990,
959, 900, 811, 768, 745, 710, 649; MS (EI, 180 °C): m/z (%) = 327.2
(10) [M+], 312.2 (14), 157.1 (100) [(M-HNTs)+], 155.1 (14), 101.1 (17)
[(M-HNTs – tBu)+], 91.1 (34), 87.0 (16), 69.1 (13), 57.1 (35) [tBu+], 55.1
126.6 (Ar-CH), 129.4 (Ar-CH), 141.0 (Ar-C), 142.9 (Ar-C); IR (ATR):
ν (cm–1) = 2934, 1398, 1369, 1298, 1283, 1254, 1203, 1145, 1055,
˜
966, 891, 848, 810, 771, 743, 710, 666; MS (EI, 130 °C): m/z (%) =
343.3 (43) [M+], 328.3 (37), 287.2 (16), 218.2 (10), 181.1 (17) 156.1
(15); HRMS (EI): calcd. for C16H25NO2N32S2 [M+]: 327.1327, found (17), 155.1 (40) [Ts+], 131.0 (17), 125.2 (31), 109.1 (11), 97.1 (17), 91.1
327.1325. 13 (2nd fraction): 1H NMR (500 MHz, CDCl3): δ = 0.85 (s, (42), 83.1 (18), 69.1 (100), 67.1 (14). 58.1 (14), 57.1 (50) [tBu+], 55.1
3
3
9 H, tBu), 1.17 (tt, J4-H,3/5-Hax = 12.1 Hz, J4-H,3/5-Heq = 2.8 Hz, 1 H,
(30); HRMS (EI): calcd. for C16H25NO3N32S2 [M+]: 343.1276, found
343.1268.
2
4-H), 1.46 (broad ddd, J3-Hax,3-Heq
13.5 Hz, 2 H, 3-Hax, 5-Hax]), 2.14 (broad d, J3-Heq,3-Hax = 14.6 Hz, 2
≈
3J3-Hax,2-Hax
≈
3J3-Hax,4-H
≈
2
4-Methylthiane 1,1-Dioxide (37). This compound was prepared in
analogy to a published procedure.[15] A solution of KMnO4 (7.45 g,
47.1 mmol) in H2O (100 mL) was added dropwise to a solution of
4-methylthiane 36[11] (1.83 g, 15.7 mmol) in CH2Cl2 (40 mL) and the
mixture was stirred overnight at r.t. Excess KMnO4 was destroyed
by addition of saturated aq. NaHSO3 solution, CH2Cl2 (100 mL) was
added, precipitated MnO2 was filtered off and was rinsed with
CH2Cl2 (200 mL). The organic layer was separated and the aqueous
layer was extracted with CH2Cl2 (100 mL). The combined organic
layers were dried (Na2SO4) and concentrated at reduced pressure
to yield 37 as a colorless solid (2.18 g, 14.7 mmol, 94 %). Rf = 0.93
2
H, 3-Heq, 5-Heq), 2.37 (s, 3 H, Ar-Me), 2.87 (broad dd, J2-Hax,2-Heq
≈
3J2-Hax,3-Hax ≈ 13.0 Hz, 2 H, 2-Hax, 6-Hax), 3.28 (broad d, J2-Heq,2-Hax
2
3
≈ 11.7 Hz, 2 H, 2-Heq,6-Heq), 7.22 (d, J = 8.1 Hz, 2 H, Ar-H), 7.77 (d,
3J = 8.2 Hz, 2 H, Ar-H); 13C NMR (125 MHz, CDCl3): δ = 21.5 (Ar-CH3),
25.1 (C-3, C-5), 27.4 [C(CH3)3], 32.6 [C(CH3)3], 45.7 (C-4), 48.0 (C-2,
C-6), 126.4 (Ar-CH), 129.4 (Ar-CH), 141.8 (Ar-C), 141.8 (Ar-C); IR (ATR):
ν (cm–1) = 2957, 1598, 1418, 1365, 1277, 1230, 1140, 1090, 1020,
˜
953, 809, 773, 757, 707, 650; MS (EI, 180 °C): m/z (%) = 327.3 (12)
[M+], 312.2 (15), 181.0 (13), 157.1 (100) [(M-HNTs)+], 155.1 (11), 131.0
(14), 101.1 (14) [(M–HNTs – tBu)+], 91.1 (24), 87.0 (15), 69.0 (31),
57.1 (31) [tBu+], 55.1 (18); HRMS (EI): calcd. for C16H25NO2N32S2 [M+]:
327.1327, found 327.1328.
(CH2Cl2/MeOH, 10:1); 1H NMR (400 MHz, CDCl3):
δ
=
1.01
= 6.5 Hz, 3 H, 4-Me), 1.69 (tqt, J4-H,3/5-Heq = 3.5 Hz,
3J4-H,4-Me = 6.9 Hz, 3J4-H,3/5-Hax = 10.8 Hz, 1 H, 4-H), 1.85 (broad dddd,
3
3
(d, J4-Me 4-H
,
cis-4-tert-Butyl-1-(4-toluenesulfonylimino)thiane 1-Oxide (15).
This compound was prepared in analogy to a published proce-
dure.[17] Cu(OTf)2 (8.9 mg, 25 μmol) was added to as suspension of
sulfoxide 11 (42.7 mg, 0.245 mmol) and PhI=NTs (101 mg,
3J3-Hax,2-Hax = 2.7 Hz, 3J3-Hax,2-Hax ≈ 3J3-Hax,4-H ≈ 11.5 Hz, 2J3-Hax,3-Heq
=
13.9 Hz, 2 H, 3-Hax, 5-Hax), 2.02 (broad d, 2J3-Heq,3-Hax = 14.1 Hz, 2 H,
3-Heq, 5-Heq), 2.90–3.04 (m, 4 H, 2-H2, 6-H2); 13C NMR (100 MHz,
0.271 mmol) in MeCN (1.5 mL). The mixture was stirred for 15 min CDCl3): δ = 21.0 (4-Me), 30.5 (C-4), 31.9 (C-3, C-5), 51.0 (C-2, C-6); IR
at r.t., concentrated at reduced pressure, and purified by column
chromatography (silica gel, cyclohexane/AcOEt, 2:1) to yield 15
(53.0 mg, 0.154 mmol, 63 %) as a colorless solid. Rf = 0.31 (cyclohex-
ane/AcOEt, 2:1); 1H NMR (400 MHz, CDCl3): δ = 0.91 (s, 9 H, tBu),
(ATR): ν (cm–1) = 2952, 2920, 1460, 1409, 1367, 1318, 1277, 1240,
˜
1197, 1115, 1066, 933, 917, 842, 708, 663; MS (FAB, 30 °C): m/z (%) =
148.1 (100) [M+], 131.1 (11) [(M-OH)+], 83.1 (46) [(M-HSO2)+], 82.1
(12), 69.1 (38), 56.0 (58), 55.0 (62), 41.0 (25), 38.9 (13); HRMS (EI):
3
3
1
1.31 (tt, J4-H,3/5-Hax = 12.2 Hz, J4-H,3/5-Heq = 2.6 Hz, 1 H, 4-H), 1.86
calcd. for C6H12O232S [M+]: 148.0558, found 148.0553. The H NMR
2
3
3
(broad ddd, J3-Hax,3-Heq ≈ J3-Hax,2-Hax ≈ J3-Hax,4-H ≈ 13.6 Hz, 2 H, 3-
data are in full agreement with published data.[39]
2
Hax, 5-Hax), 2.18 (broad d, J3-Heq,3-Hax = 14.3 Hz, 2 H, 3-Heq, 5-Heq),
rac-(2R,4R)-2,4-Dimethylthiane 1,1-Dioxide (19). BuLi (2.5M in
hexane, 3.3 mL, 8.25 mmol) was added at 0 °C to a solution of
sulfone 37 (1.00 g, 6.75 mmol) in THF (16 mL). The mixture was
stirred for 30 min at r.t. and transferred at 0 °C into a solution of
MeI (0.85 mL, 1.94 g, 13.7 mmol) in THF (16 mL). The mixture was
warmed to r.t., concentrated at reduced pressure. H2O (50 mL) was
added and the mixture was extracted with CH2Cl2 (100 mL and
3 × 50 mL). Brine (50 mL) was added to the aqueous layer, which
was additionally extracted with CH2Cl2 (50 mL). The combined or-
ganic layers were dried (Na2SO4) and concentrated at reduced pres-
sure to yield a mixture of diastereoisomers (1.08 g, 6.66 mmol,
99 %). Recrystallization (2x) from cyclohexane furnished sulfone 19
(182 mg, 1.12 mmol, 17 %) as long colorless needles. Rf = 0.05
(CH2Cl2/MeOH, 10:1); 1H NMR (500 MHz, CDCl): δ = 0.92 (d,
2
3
2.39 (s, 3 H, Ar-Me), 3.21 (ddd, J2-Hax,2-Heq ≈ J2-Hax,3-Hax ≈ 13.9 Hz,
3J2-Hax,3-Heq = 3.0 Hz, 2 H, 2-Hax, 6-Hax), 3.70 (broad d, J2-Heq,2-Hax
≈
2
3
13.4 Hz, 2 H, 2-Heq, 6-Heq), 7.26 (d, J = 8.1 Hz, 2 H, Ar-H), 7.85 (d,
3J = 8.2 Hz, 2 H, Ar-H); 13C NMR (100 MHz, CDCl3): δ = 21.6 (Ar-CH3),
23.6 (C-3, C-5), 27.4 [C(CH3)3], 32.8 [C(CH3)3], 45.8 (C-4), 52.9 (C-2,
C-6), 126.7 (Ar-CH), 129.4 (Ar-CH), 140.9 (Ar-C), 142.9 (Ar-C); IR (ATR):
ν (cm–1) = 2928, 1399, 1301, 1282, 1229, 1204, 1180, 1145, 1092,
˜
1053, 1003, 962, 891, 849, 807, 768, 755, 705, 670, 653; MS (EI,
150 °C): m/z (%) = 344.3 (14) [[M + H]+], 343.1 (72) [M+], 330.3 (10),
329.3 (20), 328.3 (100), 286.2 (12) [(M – tBu)+], 181.1 (26), 155.1 (19),
150.1 (11) [Ts+], 131.0 (30), 91.1 (33), 69.0 (58), 57.1 (25) [tBu+], 55.1
(17); HRMS (EI): calcd. for C16H25NO3N32S2 [M+]: 343.1276, found
343.1271.
trans-4-tert-Butyl-1-(4-toluenesulfonylimino)thiane
1-Oxide 3J4-Me,4-H = 6.5 Hz, 3 H, 4-Me), 1.23 (d, 3J2-Me,2-H = 6.8 Hz, 3 H, 2-Me),
(16). This compound was prepared in analogy to a published proce-
dure.[17] Cu(OTf)2 (33 mg, 91 μmol) was added to as suspension of
sulfoxide 10 (160 mg, 0.918 mmol) and PhI=NTs (377 mg,
1.01 mmol) in MeCN (6 mL). The mixture was stirred for 15 min
at r.t., concentrated at reduced pressure, and purified by column
chromatography (silica gel, cyclohexane/AcOEt, 3:1) to yield 16
1.52 (ddd 2J3-Hax,3-Heq ≈ 3J3-Hax,2-H ≈ 3J3-Hax,4-H ≈ 12.1 Hz, 1 H, 3-Hax),
2
3
1.65 (ddqdd, J4-H,3-Hax
≈
2J4-H,5-Hax ≈ 12.0 Hz, J4-H,4-Me = 6.0 Hz,
2J4-H,3-Heq ≈ J4-H,5-Heq ≈ 3.0 Hz, 1 H, 4-H), 1.71–1.83 (m, 2 H, 3-Heq
,
2
5-Hax), 1.98 (ddddd, J5-Heq,5-Hax = 14.0 Hz, 3J5-Heq,4-Hax ≈ 3J5-Heq,6-Hax
2
≈
3J5-Heq,6-Heq
≈
4J5-Heq,3-Heq ≈ 3.3 Hz, 1 H, 5-Heq), 2.85 (ddd,
2J6-Hax,6-Heq ≈ 3J6-Hax,5-Hax ≈ 13.8 Hz, J6-Hax,5-Heq = 3.8 Hz, 1 H, 6-Hax,
3
3
3
(160 mg, 0.466 mmol, 51 %) as a colorless solid. Rf = 0.29 (cyclohex-
partly covered), 2.90 (dqd, J2-Hax,3-Hax = 12.8 Hz, J2-H,2-Me = 6.5 Hz,
3.5 Hz, H, 2-H, partly covered), 2.97 (ddd,
2J6-Heq,6-Hax = 14.2 Hz, J6-Heq,5-Hax 3J6-Heq,5-Heq ≈ 3.6 Hz, 1 H, 6-
1
ane/AcOEt, 2:1); H NMR (400 MHz, CDCl3): δ = 0.91 (s, 9 H, 4-tBu), 3J2-Hax,3-Heq
=
1
3
3
3
1.28 (tt, J4-H,3/5-Hax = 12.2 Hz, J4-H,3/5-Heq = 2.8 Hz, 1 H, 4-H), 1.99
≈
Eur. J. Org. Chem. 2020, 1–11
8
© 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim