4388 J . Org. Chem., Vol. 61, No. 13, 1996
Scommoda et al.
in n-hexane) at -78 °C. The reaction mixture was stirred for
15 min at -78 °C, and ClCOOMe (0.80 mL, 10.3 mmol) was
added dropwise. After 5 min the cooling bath was removed,
and the reaction mixture was stirred for 1 h at room temper-
ature. After the mixture was cooled to -78 °C, KOt-Bu (1.16
g, 10.3 mmol) in THF (10 mL) was added. The reaction
mixture was warmed to room temperature overnight, and
saturated aqueous NH4Cl was added. The mixture was
extracted with EtOAc, and the combined organic extracts were
dried (MgSO4) and concentrated in vacuum. The residue was
dissolved in CH3CN (40 mL), and DBU (3.0 mL, 20.0 mmol)
was added at room temperature. After the dark red reaction
mixture had been stirred for 39 h at room temperature under
an atmosphere of dry argon, saturated aqueous NH4Cl was
added. The mixture was extracted with EtOAc, dried (MgSO4),
and concentrated in vacuum. Purification of the residue by
chromatography (50% n-hexane-EtOAc) gave the allylic sul-
foximine 16 (1.14 g, 31%) as a light yellow oil and the allylic
sulfoximine 15 (1.94 g, 52%) as a colorless, waxy solid.
Analytical data for 15: mp 71 °C; [R]D +68.8 (c 1.47, THF);
1H NMR (500 MHz, CDCl3) δ 7.89-7.86 (m, 2 H, o-PhS), 7.64-
7.54 (m, 3 H, m,p-PhS), 7.29-7.16 (m, 6 H), 7.11-7.04 (m, 4
H, o-PhCH2, o-PhCHdC), 6.21 (sbr, J C,H ) 154.3 Hz, 1 H,
CdCH f o-PhS (s), CdCH f p-PhS (s), CH2CH3 f CdCH
(s), CH2CH3 f CH2CH3 (s), CH2CH3 f m-PhS (s); 13C NMR
(75 MHz, CDCl3) δ 158.58 (u), 139.44 (u), 136.78 (u), 131.76
(d), 129.18 (d), 128.79 (d), 128.53 (d), 127.77 (d), 127.77 (d),
127.64 (d), 34.13 (u), 29.18 (d), 11.79 (d); MS (EI) m/ z (relative
intensity) 286 (M+ + H, 12), 285 (M+, 50), 284 (16), 237 (11),
231 (55), 206 (13), 191 (11), 179 (24), 178 (10), 165 (10), 160
(60), 145 (15), 144 (16), 132 (52), 131 (64), 130 (18), 129 (22),
128 (21), 117 (17), 116 (17), 115 (35), 107 (15), 106 (100), 91
(95), 79 (11), 78 (16), 77 (45), 65 (17), 53 (12), 51 (25), 42 (28),
41 (14), 39 (10); HRMS (EI) calcd for C17H19NOS 285.11874,
found 285.1188. Analytical data for 20: [R]D +99.5 (c 0.97,
MeOH); 1H NMR (500 MHz, CDCl3) δ 7.98-8.00 (m, 2 H,
m-PhS), 7.51-7.59 (m, 3 H, o/p-PhS), 7.32-7.38 (m, 5 H, PhC),
6.59 (s, J C,H ) 175 Hz, 1 H, CdCH), 2.98 (dq, J AB ) 13.6, J )
7.0 Hz, 1 H, CH2CH3), 2.93 (dq, J AB ) 13.7, J ) 7.0 Hz, 1 H,
CH2CH3), 2.73 (s, 3 H, NCH3), 0.74 (t, J ) 7.5 Hz, 3 H,
1
CH2CH3); H{1H} NOE CdCH f C-Ph (s), CdCH f m-PhS
(s), CH2CH3 f CH2CH3 (s), CH2CH3 f C-Ph (s), CH2CH3
f
m-PhS (s), CH2CH3 f NCH3 (m); 13C NMR (75 MHz, CDCl3)
δ 159.01 (u), 141.36 (u), 139.33 (u), 132.94 (d), 129.99 (d),
129.74 (d), 129.30 (d), 129.22 (d), 128.34 (d), 127.27 (d), 29.92
(d), 23.57 (u), 12.82 (d); MS (EI) m/ z (relative intensity) 285
(M+, 20), 238 (19), 237 (100), 222 (25), 207 (15), 206 (83), 205
(71), 204 (10), 191 (13), 132 (14), 131 (27), 130 (17), 129 (54),
128 (26), 125 (22), 117 (19), 116 (16), 115 (42), 107 (17), 106
(23), 105 (19), 103 (12), 91 (95), 78 (15), 77 (38), 65 (14), 51
(23), 42 (19); HRMS (EI) calcd for C17H19NOS 285.11874, found
285.11870
PhCHdC), 3.87 (d, J AB ) 13.47 Hz, 1 H, CH2S), 3.80 (d, J AB
)
13.73 Hz, 1 H, CH′2S), 3.78 (d, J AB ) 15.41 Hz, 1 H, PhCH2),
3.67 (d, J AB ) 15.41 Hz, 1 H, PhCH′2), 2.74 (s, 3 H, NCH3);
1H{1H} NOE NCH3 f o-PhS (m), CH2S f PhCHdC (s),
PhCHdC f CH2S (m), PhCHdC f CH′2S (m), PhCHdC f
o-PhCHdC (s); 13C NMR (75 MHz, CDCl3) δ 138.40 (u), 137.05
(u), 136.37 (u), 136.44 (d), 132.95 (d), 130.00 (d), 129.45 (u),
129.25 (d), 128.94 (d), 128.70 (d), 128.38 (d), 127.41 (d), 126.50
(d), 62.67 (u), 36.20 (u), 29.93 (d); MS (EI) m/ z (relative
(+)-(S)-N-Ben zyl-S-m eth yl-S-p h en ylsu lfoxim in e (22). A
solution of sulfoximine 21 (776 mg, 5.0 mmol) in DME (10 mL)
was added to a suspension of potassium hydride (629 mg, 5.5
mmol, 35% suspension in mineral oil) in DME (10 mL). The
resulting suspension was stirred for 30 min at room temper-
ature. Then solid n-Bu4NBr (80 mg, 0.25 mmol) and benzyl
bromide (1.28 g, 7.5 mmol) were added. The reaction mixture
was stirred for 2 h at room temperature, and ice cold 2 M
sulfuric acid was added slowly until a pH of 1.0 was reached.
Ether was added, and the organic phase was separated. The
aqueous phase was neutralized by careful addition of solid Na2-
CO3 and extracted with EtOAc. The combined organic extracts
were dried (MgSO4) and concentrated in vacuum. Purification
of the residue by chromatography (EtOAc) gave sulfoximine
22 (986 mg, 78%) as a light yellow oil: [R]D +68.4 (c 1.82,
MeOH); 1H NMR (300 MHz, CDCl3) δ 7.95-7.91 (m, 2 H),
7.64-7.50 (m, 3 H), 7.38-7.15 (m, 5 H), 4.17 (d, J AB ) 14.17
Hz, 1 H), 3.99 (J AB ) 14.17 Hz, 1 H), 3.10 (s, 3 H); 13C NMR
(75 MHz, CDCl3) δ 141.20 (u), 139.45 (u), 132.87 (d), 129.40
(d), 128.60 (d), 128.20 (d), 127.55 (d), 126.48 (d), 47.31 (u), 45.26
(u); MS (EI) m/ z (relative intensity) 245 (M+, 75), 244 (69),
168 (23), 141 (98), 140 (85), 126 (21), 125 (100), 124 (18), 105
(76), 97 (24), 91 (77), 77 (66), 65 (26), 51 (42). Anal. Calcd for
C14H15NOS: C, 68.54; H, 6.16; N, 5.71. Found: C, 68.35; H,
6.21; N, 5.88.
intensity) 361 (M+, 0.08), 91 (100). Anal. Calcd for C23H23
-
NOS: C, 76.42; H, 6.41; N, 3.87. Found: C, 76.26; H, 6.72;
1
N, 4.03. Analytical data for 16: [R]D +3.2 (c 1.18, THF); H
NMR (500 MHz, CDCl3) δ 7.71-7.67 (m, 2 H, o-PhS), 7.54-
7.50 (m, 1 H, p-PhS), 7.44-7.39 (m, 2 H, m-PhS), 7.31-7.27
(m, 2 H, m-PhCH2), 7.23-7.15 (m, 6 H, m,p-PhCHdC, m,p-
PhCH2), 7.01-6.98 (m, 2 H, o-PhCHdC), 6.65 (sbr, J C,H ) 155
Hz, 1 H, PhCHdC), 4.08 (d, J AB ) 14.04 Hz, 1 H, CH2S), 4.01
(d, J AB ) 14.04 Hz, 1 H, CH′2S), 3.84 (d, J AB ) 14.65 Hz, 1 H,
PhCH2), 3.69 (d, J AB ) 14.96 Hz, PhCH′2), 2.68 (s, 3 H, NCH3);
1H{1H} NOE NCH3 f o-PhS (m), PhCH2 f PhCHdC (m),
PhCH2 f o-PhCH2 (m), PhCHdC f o-PhCHdC (s), PhCHdC
f o-PhCH2 (m), o-PhCHdC f PhCHdC (s); 13C NMR (125
MHz, CDCl3) δ 138.69 (u), 137.85 (u), 136.11 (u), 135.36 (d),
132.72 (d), 130.53 (u), 129.39 (d), 129.22 (d), 128.57 (d), 128.32
(d), 128.29 (d), 127.07 (d), 126.55 (d), 56.56 (u), 43.11 (u), 29.74
(d); MS (EI) m/ z (relative intensity) 361 (M+, 0.17); 91 (100).
Anal. Calcd for C23H23NOS: C, 76.42; H, 6.41; N, 3.87.
Found: 76.24; H, 6.54; N, 3.87.
(+)-(S,Z)-N-Met h yl-S-p h en yl-S-(2-p h en yl-1-b u t en yl)-
su lfoxim in e (19) a n d (+)-(S,E)-N-Meth yl-S-p h en yl-S-(2-
p h en yl-1-bu ten yl)su lfoxim in e (20). To a solution of hy-
droxysulfoximine 5 (3.45 g, 11.4 mmol) (diastereomeric mixture)
in THF (40 mL) was added n-BuLi (11.4 mmol, 7.5 mL of 1.52
M in n-hexane) at -78 °C. The resulting yellow solution was
stirred at this temperature for 1 h and cooled to -85 °C, and
ClCOOMe (0.88 mL, 11.4 mmol) was added. The solution was
stirred at room temperature for 30 min and cooled to -78 °C,
and KOt-Bu (1.28 g, 11.4 mmol) in THF (10 mL) was added
dropwise. After the solution had been stirred for 45 min at
this temperature and 45 min at room temperature, saturated
aqueous NH4Cl was added. The mixture was extracted with
EtOAc. The combined organic extracts were dried (MgSO4)
and concentrated in vacuum. Purification of the residue by
chromatography (50% EtOAc-n-hexane) gave sulfoximine 20
(916 mg, 28%) and sulfoximine 19 (1.38 g, 42%) as colorless
oils. Analytical data for 19: [R]D +59.5 (c 1.53, MeOH); 1H
NMR (500 MHz, CDCl3) δ 7.35-7.39 (m, 3 H, o/ p-PhS), 7.22-
7.26 (m, 2 H, m-PhS), 7.17-7.20 (m, 1 H, p-PhC), 7.10-7.14
(S,2R)- an d (S,2S)-1-(N-Ben zyl-S-ph en ylsu lfon im idoyl)-
2-m eth yl-3-p h en ylp r op a n -2-ol (25). To a solution of sul-
foximine 22 (2.15 g, 8.7 mmol) in THF (40 mL) was added
n-BuLi (8.7 mmol, 5.84 mL of 1.5 M in n-hexane) at -10 °C.
The resulting orange solution was cooled to -78 °C, and
phenylacetone (1.18 g, 8.7 mmol) in THF (10 mL) was added.
The reaction mixture was slowly warmed to 0 °C (3 h) and
then diluted with saturated aqueous NH4Cl. The organic
phase was separated, and the aqueous phase was extracted
with EtOAc. The combined organic phases were dried (MgSO4)
and concentrated in vacuum. The residue was purified by
chromatography (EtOAc), and the excess of phenylacetone was
removed in vacuum at 50 °C (10-4 Torr). A mixture of
hydroxysulfoximine (S,2R)-25 and hydroxysulfoximine (S,2S)-
25 (2.32 g, 70%) was obtained as a viscous oil. Analytical data
are given for the mixture of diastereomers (I, major diastere-
omer; II, minor diastereomer): 1H NMR (300 MHz, CDCl3) δ
7.95-7.90 (m, 2 H, II), 7.88-7.82 (m, 2 H, I), 7.65-7.14 (m,
13 H), 6.84 (s, 1 H), 4.30 (d, J AB ) 14.51 Hz, 1 H, II), 4.19 (d,
J AB ) 14.51 Hz, 1 H, I), 4.01 (d, J AB ) 14.51 Hz, 1 H, II), 3.89
(m, 2 H, m-PhC), 6.85-6.88 (m, 2 H, m-PhS), 6.59 (m, J C,H
175 Hz, 1 H, CdCH), 2.57 (s, 3 H, NCH3), 2.38 (dqd, J AB
)
)
16.0, J ) 7.3, 1.5 Hz, 1 H, CH2CH3), 2.34 (dqd, J AB ) 16.2, J
) 7.3, 1.5 Hz, 1 H, CH2CH3), 1.02 (t, J ) 7.3 Hz, 3 H, CH2CH3);
1H{1H} NOE CdCH f CH2CH3 (s), CdCH f CH2CH3 (s),
(d, J AB ) 14.51 Hz, 1 H, I), 3.44-3.18 (m, 3 H), 3.03 (d, J AB
)
13.83 Hz, 1 H, II), 2.80 (m, 2 H, I), 1.71 (s, 3 H, I), 1.11 (s, 3