246 Abrunhosa-Thomas et al.
(dd, 2 JHH = 10.9 Hz, 3 JHH = 8.7 Hz, 1H, SCHH), 4.03
ing mixture was stirred until completion (about
1 h, monitored by TLC). The solvent was evap-
orated, and the product was purified by column
chromatography.
3
3
(dd, JHH = 10.7 Hz, JHH = 8.7 Hz, 1H, CHtBu),
7.25–7.34 and 7.51–7.55 (m, 5H, C6H5). 13C NMR
(CDCl3, 101 MHz): δ = 26.8 (C(CH3)3), 28.2 and
28.8 (C(CH3)2), 34.6 (SCH2), 35.0 (C(CH3)3), 52.3
(C(CH3)2), 87.3 (CHtBu), 128.6 (C6H5), 128.9 (C6H5),
132.1 (Cipso), 136.2 (C6H5), 174.4 (SCN).
(S) - 4 - Benzyl - 2 - [2 - phenylsulfanyl - 2 - methy-
lpropyl]thiazoline (5a): Prepared by the general pro-
cedure from 4a and thiophenol, purified by chro-
matography on silica gel (eluent: pentane/Et2O 95:5);
(S)-4-Benzyl-2-(1-phenylsulfanyl-1-methylethyl)-
thiazoline (2c): Prepared by the general procedure
from 1c and diphenyl disulfide, purified by chro-
matography on silica gel (eluent: pentane/Et2O 95:5);
yellow oil, 65% yield. 1H NMR (CDCl3, 250 MHz) δ =
1.57 and 1.59 (2s, 6H, C(CH3)2), 2.53 (dd, 2 JHH = 13.6,
1
yellow oil, 64% yield, [α]2D0 −79 (c 1, acetone). H
NMR (CDCl3, 250 MHz) δ = 1.46 and 1.48 (2s, 6H,
2
3
(CH3)2C), 2.51 (dd, JHH = 13.6, JHH = 9.2, 1H,
2
CHHPh), 2.64 (s, 2H, CH2C N), 3.07 (dd, JHH
=
13.6, JHH = 4.9, 1H, CHHPh), 3.35 (dd, 3 J = 9.4,
3
2 JHH = 10.9, 1H, CHHS), 3.51 (dd, JHH = 8.8,
3
3 JHH = 9.3, 1H, CHHPh), 3.00 (dd, 2 JHH = 13.6, 3 JHH
=
2 JHH = 10.9, 1H, CHHS), 4.62 (m, 1H, CHN), 7.26–
7.63 (m, 10Har). 13C NMR (CDCl3, 63 MHz) δ =
27.6 and 28.1 (CH3), 37.6 (CH2Ph), 42.8 (CH2S),
44.1 (CH2C N), 47.6 (C(CH3)2), 80.3 (CHPh), 125.6,
126.5, 127.7, 142.2, 170.8 (S C N).
2
3
4.9, 1H, CHHPh), 3.01 (dd, JHH = 11.1, JHH = 6.2,
2
3
1H, CHHS), 3.18 (dd, JHH = 11.1, JHH = 8.5, 1H,
CHHS), 4.59 (m, 1H, CHN), 7.11–7.35 and 7.54–7.58
(m, 10H, Har). 13C NMR (CDCl3, 63 MHz) δ = 28.2
and 28.3 (C(CH3)2), 37.4 (CH2Ph), 39.8 (CH2S), 51.8
(C(CH3)2), 78.3 (CHN), 126.4, 128.4, 128.6, 129.3,
129.4, 131.7, 136.3, 138.5, 176.3 (S C N). IR (cm−1):
3010, 2960, 2920, 2850, 1640, 1490, 1450, 1030.
(R,Rs)-4-Ethyl-2-(1-tert-butylsulfinyl-1-methy-
lethyl)thiazoline (3a): Prepared by the gen-
eral procedure from 1a and (R)-tert-butyl-tert-
butanethiosulfinate, purified by chromatography on
silica gel (eluent: pentane/AcOEt 50:50), [α]2D0 +128
(R) - 4 - Phenyl - 2 - [2 - phenylsulfanyl - 2methy-
lpropyl]thiazoline (5b): Prepared by the general pro-
cedure from 4b and thiophenol, purified by chro-
matography on silica gel (eluent: pentane/Et2O 95:5);
1
yellow oil, 68% yield. H NMR (CDCl3, 250 MHz)
δ (ppm): 1.45 and 1.50 (2s, 6H, (CH3)2C), 2.64
3
(s, CH2C N), 3.35 (t, JHH = 7.50, 1H, CHHS),
3
2
3.42 (dd, JHH = 7.5, JHH = 10.0, 1H, CHHS),
3
1
5.46 (t, JHH = 10.0, 1H, CHN), 7.26–7.63 (m,
(c 0.9, acetone). H NMR (CDCl3, 400 MHz): δ =
10Har). 13C NMR (CDCl3, 63 MHz) δ (ppm): 27.9
(CH3), 28,8(CH3), 42.8 (CH2S), 44.2 (CH2C N), 47.8
(C(CH3)2), 80.3 (CHPh), 125.6, 126.5, 127.7, 142.2,
171.5 (S C N). IR (cm−1): 2900, 1600, 1440, 1020.
Anal. calcd for: C19H21NS2: C, 69.68%; H, 6.46%; N,
4.28; S 19.58%. Found: C, 69.62%; H, 6.46%; N, 4.38;
S 19.32%.
3
1.01 (t, JHH = 7.4 Hz, 3H, CH2CH3), 1.31 (s, 9H,
C(CH3)3), 1.53–1.89 (m, 2H, CH2CH3), 1.57 (s, 3H,
2
C(CH3)2), 1.59 (s, 3H, C(CH3)2), 2.95 (dd, JHH
=
11.0 Hz, 3 JHH = 8.0 Hz, 1H, SCHH), 3.32 (dd, 2 JHH
=
3
11.0 Hz, JHH = 8.6 Hz, 1H, SCHH), 4.28–4.36 (m,
1H, CHEt). ES-MS m/z (%): 262 (M + H, 21), 157
(100), 156 (32).
(R)-4-Phenyl-2-[2-ethylsulfanyl-2methylpropyl]-
thiazoline (5c): Prepared by the general procedure
from 4b and ethanethiol, purified by chromatogra-
phy on silica gel (eluent: pentane/Et2O 95:5); yellow
(R,Ss)-4-Ethyl-2-(1-tert-butylsulfinyl-1-methy-
lethyl)thiazoline (3a): Prepared by the gen-
eral procedure from 1a and (S)-tert-butyl-tert-
butanethiosulfinate, purified by chromatography on
silica gel (eluent: pentane/AcOEt 50:50), [α]2D0 −117
1
oil, 52% yield. H NMR (CDCl3, 250 MHz) δ (ppm):
3
1
1.25 (t, JHH = 7.4, 3H, CH3CH2), 1.46 and 1.47 (2s,
(c 1.1, acetone). H NMR (CDCl3, 400 MHz): δ =
6H, (CH3)2C), 2.62 (q, 3 JHH = 7.4, 2H, CH2CH3), 2.98
3
1.00 (t, JHH = 7.4 Hz, 3H, CH2CH3), 1.29 (s, 9H,
2
3
(s, 2H, CH2C N), 3.20 (dd, JHH = 10.9, JHH = 9.9,
C(CH3)3), 1.54–1.88 (m, 2H, CH2CH3), 1.55 (s, 3H,
2
3
2
1H, CHHS), 3.68 (dd, JHH = 10.9, JHH = 8.9, 1H,
C(CH3)2), 1.59 (s, 3H, C(CH3)2), 2.89 (dd, JHH
=
3
11.0 Hz, 3 JHH = 8.9 Hz, 1H, SCHH), 3.33 (dd, 2JHH
=
CHHS), 5.46 (t, JHH = 9.0, 1H, CHN), 7.26–7.36
(m, 5Har). 13C NMR (CDCl3, 63 MHz) δ (ppm): 13.3
(CH3CH2), 21.3 (CH2CH3), 27.8 and& 28.1 (2CH3),
40.8 (CH2S), 43,0 (CH2C N), 45.8 ((CH3)2C), 79.1
(CHN), 125.6, 126.5, 127.6, 141.1, 167.1 (S C N).
3
11.0 Hz, JHH = 8.6 Hz, 1H, SCHH), 4.26–4.34 (m,
1H, CHEt). ES-MS m/z (%): 262 (M + H, 22), 157
(100), 156 (25).
Synthesis of β-Sulfanyl Thiazolines 5
Synthesis of (S)-4-Methylsulfanylethyl-2-phenyl-
2-thiazoline 8
General Procedure. Thiophenol (1.2 mmol) and
then NEt3 (0.1 mmol) were added to the α,β-
unsaturated thiazoline 4 (1 mmol), dissolved in dry
THF (20 mL), at room temperature. The result-
Step 1: Thioacylation. Thioamide 7 was pre-
pared from dithiobenzoic acid methyl ester (420 mg,
Heteroatom Chemistry DOI 10.1002/hc