Bayer et al.
m, 3H), 3.43-3.40 (2H, m, 6H), 1.48 (3H, d, J ) 7.0 Hz, Me);
13C NMR δ 153.5, 135.2, 130.7, 128.7, 128.6, 128.3, 112.0, 68.7,
49.8, 48.6, 22.2; IR (neat) ν 3034 (m), 2933 (m), 1713 (s), 1604
(w), 1496 (w), 1390 (s), 1299 (s), 1109 (s), 1087 (s); EIMS m/z
(relative intensity) 265 (M+, 0.8), 91 (100). Anal. Calcd for
(2H, s, Bn), 4.41 (1H, m, 3H), 3.45 (1H, m, 6H), 1.48 (3H, d, J
) 6.2 Hz, 3Me), 1.35 (3H, d, J ) 7.3 Hz, 6Me);
13C NMR δ
155.8, 135.3, 132.2, 128.7, 128.5, 128.1, 119.1, 69.0, 54.1, 49.2,
22.2, 16.6; IR (KBr tablet) ν 3034 (w), 2973 (m), 2931 (m), 1723
(s), 1497 (w), 1273 (s), 1244 (s), 1104 (s); EIMS m/z (relative
intensity) 279 (M+, 0.4), 91 (100). Anal. Calcd for C14H17
-
C
13H15NO3S: C, 58.85; H, 5.70; N, 5.28. Found: C, 58.63; H,
5.71; N, 5.15.
NO3S: C, 60.19; H, 6.13; N, 5.01. Found: C, 59.89; H, 6.40;
N, 4.90.
Ben zyl (1R*,3R*)-3,6-Dih yd r o-3-m eth yl-1λ4,2-th ia zin e-
2-ca r boxyla te 1-Oxid e (tr a n s-11a ). FC (Et2O/pentane, 80/
20) of the crude product afforded trans-11a as colorless oil.
Analytical data for trans-11a : HPLC (Chiralcel OJ , iPrOH/
hexane, 60/40, 0.7 mL min-1, 230 nm) tR 12.0 and 20.5 min;
1H NMR δ 7.41-7.33 (5H, m, Bn), 6.37 (1H, ddd, J ) 9.8, 6.2,
2.9 Hz, 4H), 5.86 (1H, ddd, J ) 9.8, 7.4, 2.9 Hz, 5H), 5.31 (1H,
AB, J ) 12.2 Hz, Bn), 5.24 (1H, AB, J ) 12.2 Hz, Bn), 4.62
(1H, pent, J ) 6.2 Hz, 3H), 3.52 (1H, dAB, J ) 15.3, 7.5 Hz,
6H), 3.40 (1H, mAB, J ) 15.3 Hz, 6H), 1.35 (3H, d, J ) 6.2
Hz, Me); 13C NMR δ 154.7, 135.3, 134.4, 128.7, 128.5, 128.2,
114.2, 69.0, 50.2, 47.2, 20.2; IR (KBr tablet) ν 3032 (m), 2971
(m), 2931 (m), 1713 (s), 1497 (m), 1454 (m), 1384 (s), 1283 (s),
1097 (s), 1065 (s); EIMS m/z (relative intensity) 265 (M+, 0.6),
91 (100). Anal. Calcd for C13H15NO3S: C, 58.85; H, 5.70; N,
5.28. Found: C, 58.67; H, 5.83; N, 5.41.
(1R*,3S*,6R*)-3,6-Dih yd r o-3,6-d im et h yl-2-t osyl-1λ4,2-
th ia zin e 1-Oxid e (cis-12b).13 FC (Et2O/pentane, 60/40) of the
crude product provided a mixture of cis-12b and p-toluene-
sulfonamide. All attempts to separate these compounds failed.
Data for cis-12b: HPLC (Chiralcel OJ , iPrOH/hexane, 60/40,
0.7 mL min-1, 230 nm) tR 13.7 (1S,3R,6S) and 19.0 (1R,3S,6R)
1
min; H NMR δ 7.82 (2H, d, J ) 8.4 Hz, Ts), 7.34 (2H, d, J )
8.1 Hz, Ts), 5.88 (1H, dt, J ) 11.0, 3.3 Hz, 4H), 5.40 (1H, dt,
J ) 11.0, 2.0 Hz, 5H), 4.59-4.51 (1H, m, 3H), 3.33-3.25 (1H,
m, 6H), 2.43 (3H, s, Me), 1.43 (3H, d, J ) 7.3 Hz, 6Me), 1.30
(3H, d, J ) 7.0 Hz, 3Me); 13C NMR δ 144.7, 137.7, 130.2, 129.9,
127.2, 119.7, 53.4, 50.9, 22.3, 21.7, 15.8.
(1R*,3R*,6S*)-3,6-Dih yd r o-3,6-d im et h yl-2-t osyl-1λ4,2-
th ia zin e 1-Oxid e (tr a n s-12b).13 FC (Et2O/pentane, 90/10) of
the crude product afforded trans-12b as a white solid. Analyti-
cal data for trans-12b: mp 136-137 °C (rac); HPLC (Chiralpak
AD, iPrOH/hexane, 50/50, 0.7 mL min-1, 230 nm) tR 10.7 and
24.2 min; 1H NMR δ 7.85 (2H, d, J ) 8.1 Hz, Ts), 7.34 (2H, d,
J ) 8.1 Hz, Ts), 5.80-5.72 (2H, m, 4/5H), 3.90-3.84 (1H, m,
3H), 3.49-3.42 (1H, m, 6H), 2.42 (3H, s, Me), 1.45 (3H, d, J )
6.6 Hz, 3Me), 1.38 (3H, d, J ) 7.0 Hz, 6Me); 13C NMR δ 144.9,
134.8, 131.5, 130.1, 128.2, 119.5, 55.8, 49.6, 21.7, 21.2, 17.0;
IR (KBr tablet) ν 3034 (w), 2973 (m), 2931 (m), 1495 (m), 1496
(w), 1346 (s), 1166 (s); EIMS m/z (relative intensity) 299 (M+,
0.3), 91 (100). Anal. Calcd for C13H17NO3S2: C, 52.15; H, 5.72;
N, 4.68. Found: C, 52.40; H, 5.48; N, 4.62.
(1S,3R)-3,6-Dih ydr o-3-m eth yl-2-tosyl-1λ4,2-th iazin e 1-Ox-
id e (cis-11b).12c FC (Et2O/pentane, 90/10) of the crude product
afforded cis-11b as a white solid. Analytical data for cis-11b:
[R]20 +4.7° (c 1.0, CH2Cl2); HPLC (Chiralcel OJ , iPrOH/
D
hexane, 35/65, 0.7 mL min-1, 230 nm) 54% ee, tR 22.7 (1S,3R)
and 36.5 (1R,3S) min; 1H NMR δ 7.81 (2H, d, J ) 8.4 Hz, Ts),
7.34 (2H, d, J ) 8.1 Hz, Ts), 5.97 (1H, dt, J ) 11, 3 Hz, 4H),
5.75-5.67 (1H, m, 5H), 4.62-4.55 (1H, m, 3H), 3.45 (1H, dd,
J ) 16.5, 6.6 Hz, 6H), 3.38-3.30 (1H, m, 6H), 2.43 (3H, s, Ts),
1.34 (3H, d, J ) 7.0 Hz, Me); 13C NMR δ 144.8, 137.5, 130.5,
130.2, 127.2, 112.6, 51.1, 49.5, 22.3, 21.7; IR (KBr tablet) ν
3030 (m), 2935 (m), 1598 (m), 1496 (w), 1334 (s), 1162 (s), 1092
(s); EIMS m/z (relative intensity) 265 (M+, 3), 91 (100). Anal.
Calcd for C12H15NO3S2: C, 50.51; H, 5.30; N, 4.91. Found: C,
50.25; H, 5.57; N, 4.80. A racemic sample, (1R*,3S*)-11b,
recrystallized from CH2Cl2/heptane melted at 138-139 °C (lit.
142 °C).12c
(1R *,3S*,6R *)-3,6-Dih yd r o-6-[(b e n zyloxy)m e t h yl]-3-
m eth yl-2-tosyl-1λ4,2-th iazin e 1-Oxide (cis-13) an d (1R*,3S*,
6R*)-3,6-Dih ydr o-3-[(ben zyloxy)m eth yl]-6-m eth yl-2-tosyl-
1λ4,2-th ia zin e 1-Oxid e (cis-14). FC (EtOAc/pentane, 50/50)
provided an inseparable mixture of cis-13 and cis-14 as a pale
yellow oil. TLC Rf ) 0.56 (EtOAc/pentane, 50/50). Anal. Calcd
of the mixture C20H23NO4S2: C, 59.24; H, 5.72; N, 3.45.
Found: C, 59.40; H, 6.01; N, 3.26. Data for cis-13: HPLC
(Chiralpak AD, iPrOH/hexane, 20/80, 0.5 mL min-1, 230 nm)
(1R*,3R*)-3,6-Dih yd r o-3-m et h yl-2-t osyl-1λ4,2-t h ia zin e
1-Oxid e (tr a n s-11b).12c FC (Et2O/pentane, 90/10) of the crude
product afforded trans-11b as a colorless viscous oil. Analytical
data for trans-11b: HPLC (Chiralcel OJ , iPrOH/hexane, 35/
65, 0.7 mL min-1, 230 nm) tR 22.0 (1R,3R) and 25.7 (1S,3S)
1
tR 38.3 and 46.2 min; H NMR δ 7.82 (2H, d, J ) 8.4 Hz, Ts),
1
7.37-7.23 (7H, m, Ts/Ph), 5.91 (1H, dt, J ) 11.0, 3.3 Hz, 4H),
5.28 (1H, dt, J ) 11.0, 2.2 Hz, 5H), 4.63 (1H, AB, J ) 12.1 Hz,
Bn), 4.52 (1H, AB, J ) 12.1 Hz, Bn), 4.62-4.56 (1H, m, 3H),
3.72 (2H, d, J ) 8.4 Hz, CH2), 3.53-3.47 (1H, m, 6H), 2.43
(3H, s, Ts-Me), 1.35 (3H, d, J ) 7.0 Hz, Me); 13C NMR δ 144.7,
137.6, 137.3, 130.8, 130.2, 128.6, 127.9, 127.2, 114.5, 73.7, 68.5,
60.5, 51.8, 22.5, 21.7. Data for cis-14: HPLC (Chiralpak AD,
iPrOH/hexane, 20/80, 0.7 mL min-1, 230 nm) tR 21.6 and 22.9
min; H NMR δ 7.88 (2H, d, J ) 8.4 Hz, Ts), 7.32 (2H, d, J )
8.4 Hz, Ts), 6.05 (1H, ddd, J ) 10.2, 4.8, 2.6 Hz, 4H), 5.75
(1H, m, 5H), 4.04-3.95 (1H, m, 3H), 3.58-3.53 (2H, m, 6H),
2.43 (3H, s, Ts), 1.46 (3H, d, J ) 6.6 Hz, Me); 13C NMR δ 144.9,
134.5, 133.6, 130.0, 128.4, 113.7, 50.8, 49.1, 21.7, 20.8.
Ben zyl (1S,3R,6S)-3,6-Dih yd r o-3,6-d im eth yl-1λ4,2-th i-
a zin e-2-ca r boxyla te 1-Oxid e (cis-12a ).3 FC (Et2O/pentane,
60/40) of the crude product afforded cis-12a as a white solid.
1
Analytical data for cis-12a : [R]20 -15° (c 1, CH2Cl2); HPLC
min; H NMR δ 7.73 (2H, d, J ) 6.6 Hz, Ts), 7.37-7.23 (7H,
D
(Chiralcel OJ , iPrOH/hexane, 20/80, 0.7 mL min-1, 230 nm)
61% ee, tR 20.1 (1R,3S,6R) and 22.7 (1S,3R,6S) min; 1H NMR
δ 7.40-7.29 (5H, m, Bn), 5.93 (1H, dt, J ) 11.0, 2.9 Hz, 4H),
5.40 (1H, dt, J ) 11.0, 2.4 Hz, 5H), 5.28 (1H, AB, J ) 12.2 Hz,
Bn), 5.24 (1H, AB, J ) 12.2 Hz, Bn), 4.55-4.48 (1H, m, 3H),
3.37-3.29 (1H, m, 6H), 1.45 (3H, d, J ) 7.0 Hz, Me), 1.44 (3H,
d, J ) 7.0 Hz, Me); 13C NMR δ 153.5, 135.3, 130.3, 128.62,
128.61, 128.3, 119.2, 68.7, 52.1, 49.6, 22.3, 15.8; EIMS m/z
m, Ts/Ph), 6.16 (1H, dt, J ) 11.0, 3.3 Hz, 4H), 5.43 (1H, dt, J
) 11.0, 2.2 Hz, 5H), 4.69-4.60 (1H, m, 3H), 4.44 (1H, AB, J )
12.1 Hz, Bn), 4.36 (1H, AB, J ) 12.1 Hz, Bn), 3.54 (2H, d, J )
8.9 Hz, CH2), 3.28-3.24 (1H, m, 6H), 2.41 (3H, s, Ts-Me), 1.42
(3H, d, J ) 7.3 Hz, Me); 13C NMR (selected signals) δ 144.7,
137.9, 130.1, 128.5, 128.1, 127.7, 126.0, 120.6, 72.5, 53.1, 15.7.
(1R *,3R *,6S*)-3,6-Dih yd r o-6-[(b e n zyloxy)m e t h yl]-3-
m et h yl-2-t osyl-1λ4,2-t h ia zin e 1-Oxid e (tr a n s-13) a n d
(1R*,3R*,6S*)-3,6-Dih yd r o-3-[(ben zyloxy)m eth yl]-6-m eth -
yl-2-tosyl-1λ4,2-th ia zin e 1-Oxid e (tr a n s-14). FC (EtOAc/
pentane, 50/50) provided an inseparable mixture of trans-13
and trans-14 as a white solid. TLC Rf ) 0.29 (EtOAc/pentane,
50/50). Anal. Calcd of the mixture C20H23NO4S2: C, 59.24; H,
5.72; N, 3.45. Found: C, 59.07; H, 5.96; N, 3.18. Data for trans-
(relative intensity) 279 (M+, 5), 91 (100). Anal. Calcd for C14H17
-
NO3S: C, 60.19; H, 6.13; N, 5.01. Found: C, 60.42; H, 6.20;
N, 4.94. A racemic sample melted at 79-81 °C.
Ben zyl (1R*,3R*,6S*)-3,6-Dih yd r o-3,6-d im eth yl-1λ4,2-
th ia zin e-2-ca r boxyla te 1-Oxid e (tr a n s-12a ).3 FC (Et2O/
pentane, 80/20) of the crude product afforded trans-12a as a
colorless oil. Analytical data for trans-12a : HPLC (Chiralcel
OJ , iPrOH/hexane, 40/60, 0.7 mL min-1, 230 nm) tR 13.2 and
14.6 min; 1H NMR δ 7.41-7.31 (5H, m, Bn), 6.09 (1H, dd, J )
10.6, 4.8 Hz, 4H), 5.85 (1H, dd, J ) 10.6, 7.0 Hz, 5H), 5.27
13: HPLC (Chiralcel OJ , iPrOH/hexane, 60/40, 0.6 mL min-1
,
230 nm) tR 35.6 and 44.6 min; 1H NMR δ 7.84 (2H, d, J ) 7.7
Hz, Ts), 7.40-7.25 (7H, m, Ts/Ph), 5.88 (1H, dd, J ) 10.6, 3.2
Hz, 4H), 5.63 (1H, dd, J ) 10.4, 6.7 Hz, 5H), 4.58 (1H, AB, J
7204 J . Org. Chem., Vol. 69, No. 21, 2004