November 2002
1523
1-one (1b) (0.68 g, 1.46 mmol) was added dropwise to a EtOH solution of
EtONa (prepared from Na (23 mg, 1.00 mmol) and EtOH (1.00 ml)) at 0 °C.
C, 61.54; H, 4.95; N, 2.99. Found: C, 60.88; H, 4.95; N, 2.23.
Reaction of 4 with N-Phenylmaleimide A benzene (4.00 ml) solution
The work-up procedure provided (2E,4Z)-1-phenyl-5-(phenylselenenyl)-4- of 4 (0.20 g, 0.64 mmol) and N-phenylmaleimide (0.67 g, 3.9 mmol) was
(phenylsulfenyl)pent-2,4-dien-1-one (3) (0.37 g, 61%) as a yellow oil. IR heated 25 h under an Ar atmosphere. The work-up procedure gave 6-ben-
(KBr, cmꢂ1) 1680 (CO); 1H-NMR (400 MHz, CDCl3) d: 7.19 (1H, d, 1H,
zoyl-4-ethoxy-2-phenyl-3-(phenylsulfenyl)-3a,4,5,7a-tetrahydro-1H-isoin-
Jꢁ14 Hz, 2-H), 7.37 (1H, d, Jꢁ14 Hz, 3-H), 7.15—7.61 (12H, m, ArH), dole-1,3(2H)-dione (9) (137 mg, 59%) as light yellow prisms. mp 148—
7.77—7.80 (3H, m, ArH), 8.05 (1H, d, Jꢁ1 Hz, olefinic H); 13C-NMR 152 °C (dec.), IR (KBr, cmꢂ1) 1790, 1710 (CO), 1220, 1200, 1130 (ether);
(100 MHz, CDCl3) d 122.39 (d), 126.57 (d), 128.07 (dꢃ2), 128.39 (s),
128.57 (dꢃ2), 128.71 (dꢃ2), 128.78 (d), 129.47 (dꢃ2), 129.86 (dꢃ2),
1H-NMR (400 MHz, CDCl3) d: 1.20 (3H, t, Jꢁ7 Hz, Me), 2.75 (1H, dd,
Jꢁ10, 17 Hz, 3-H), 2.82—2.88 (1H, m, 3-H), 3.75—3.85 (3H, m, 1-H, 2-H,
132.88 (d), 133.54 (dꢃ2), 133.88 (s), 138.44 (s), 142.98 (d), 153.93 (d), 6-H), 3.96—4.03 (2H, m, OCH2), 7.13—7.21 (3H, m, ArH), 7.23—7.42
190.62 (s); MS m/z 265 (MꢀꢂPhSe). Anal. Calcd for C23H18OSSe: C, 65.55; (6H, m, ArH), 7.44—7.63 (4H, m, ArH), 7.88 (2H, dd, Jꢁ1, 8 Hz, ArH);
H, 4.31 Found: C, 65.18; H, 4.41.
13C-NMR (100 MHz, CDCl3) d: 15.43 (q), 25.48 (t), 42.59 (d), 43.26 (d),
Preparation of (2E,4Z)-4-Ethoxy-1-phenyl-5-(phenylsulfenyl)pent- 45.49 (d), 64.90 (t), 126.29 (dꢃ2), 126.37 (dꢃ2), 128.20 (dꢃ2), 128.66
2,4-dien-1-one (4) A EtOH (4 ml) solution of (Z)-3,4-diethoxy-5-(phenyl- (dꢃ2), 129.13 (dꢃ3), 129.52 (dꢃ2), 129.91 (s), 131.63 (s), 133.10 (d),
sulfenyl)pent-4-enophenone (2c) (1.45 g, 4.07 mmol) was added dropwise to
a EtOH solution of EtONa (prepared from Na (115 mg, 5.00 mmol) and
133.10 (d), 136.82 (s), 158.87 (s), 173.58 (s), 174.56 (s), 199.06 (s); MS m/z
483 (Mꢀ). Anal. Calcd for C29H25NO4S: C, 72.03; H, 5.21; N, 2.90. Found:
EtOH (8 ml)) at 0 °C. The work-up procedure provided (2E,4Z)-4-ethoxy-1- C, 70.96; H, 5.25; N, 2.44.
phenyl-5-(phenylsulfenyl)pent-2,4-dien-1-one (4) (4Z : 4Eꢁ95 : 5) (1.12 g,
Reaction of (2E,4Z)-1-Phenyl-5-(phenylselenenyl)-4-(phenylsulfenyl)-
89%) as a yellow oil. IR (KBr, cmꢂ1) 1660 (CO), 1210 (ether); 1H-NMR pent-2,4-dien-1-one (3) and Dimethyl Acetylenedicarboxylate A ben-
(400 MHz, CDCl3) d: 1.45 (t, Jꢁ7 Hz, 4Z-Me), 4.02 (q, Jꢁ7 Hz, 4E-OCH2), zene (2.00 ml) solution of 3 (0.15 g, 0.35 mmol) and dimethyl acetylenedi-
4.07 (q, Jꢁ7 Hz, 4Z-OCH2), 5.81 (s, 4E-olefinic H), 6.46 (s, 4Z-olefinic H),
7.11 (d, Jꢁ15 Hz, 4Z-olefinic H), 7.14 (d, Jꢁ15 Hz, 4Z-olefinic H), 7.19—
7.59 (m, ArH), 7.93—7.99 (m, 4E-olefinic and ArH); 13C-NMR (100 MHz,
carboxylate (0.35 g, 2.49 mmol) was heated 18 h under an Ar atmosphere.
The work-up procedure gave dimethyl 3-benzoyl-5-(phenylsulfenyl)phtha-
late (13) (63 mg, 44%) as a yellow oil: IR (KBr, cmꢂ1) 1730, 1709 (CO); 1H-
CDCl3) d: 16.00 (q), 67.53 (t), 119.49 (d), 126.03 (d), 127.87 (dꢃ2), 128.61 NMR (400 MHz, CDCl3) d 3.64 (3H, s, Me), 3.87 (3H, s, Me), 7.32—7.47
(dꢃ2), 128.83 (dꢃ2), 129.61 (dꢃ2), 130.27 (d), 132.92 (d), 133.05 (s), (8H, m, ArH), 7.54—7.59 (1H, m, ArH), 7.67—7.71 (2H, m ArH), 7.77
134.80 (s), 139.02 (d), 205.85 (s); HR-MS. Calcd for C19H18O2S: 310.1027, (1H, br d, Jꢁ2 Hz, ArH); 13C-NMR (100 MHz, CDCl3) d: 52.85 (q), 53.14
found m/z 310.1033.
Reaction of 2 with N-Phenylmaleimide A benzene (1.50 ml) solution
(q), 128.69 (dꢃ2), 129.28 (d), 130.09 (dꢃ2), 130.89 (d), 131.09 (s), 131.28
(d), 131.69 (s), 131.96 (s), 133.76 (dꢃ2), 136.30 (s), 139.60 (s), 141.82 (s),
of 2 (4Z : 4Eꢁ86 : 14) (100 mg, 0.28 mmol) and N-phenylmaleimide (0.49 g, 166.28 (s), 167.44 (s), 194.99 (s); HR-MS. Calcd for C23H18O5S: 406.0875,
2.80 mmol) was heated 7 h under an Ar atmosphere. The solvent was re- found m/z 406.0915.
moved under reduced pressure. The residue was purified by preparative TLC
Reaction of 3 with Benzoquinone A toluene (2.00 ml) solution of 3
on silica gel eluting with AcOEt–n-hexane (1 : 5) to give 7-benzoyl-5- (0.15 g, 0.36 mmol) and 1,4-benzoquinone (1.27 g, 2.5 mmol) was heated
ethoxy-2-phenyl-4-(phenylselenenyl)-3a,4,5,7a-tetrahydro-1H-isoindole-
1,3(2H)-dione (5) (73 mg, 49%) as white prisms. mp 163—167 °C (dec.); IR
(KBr, cmꢂ1) 1780, 1710 (CO), 1210, 1130 (ether); 1H-NMR (400 MHz,
93 h under an Ar atmosphere. The work-up procedure gave 5-benzoyl-7-
(phenylsulfenyl)-1,4-naphthoquinone (14) (38 mg, 29%) as dark yellow
prisms. mp 163—166 °C; IR (KBr, cmꢂ1) 1717, 1672 (CO); 1H-NMR
CDCl3) d: 1.19 (3H, t, Jꢁ7 Hz, Me), 2.65-2.73 (1H, m, 6-H), 2.80—2.88 (400 MHz, CDCl3) d 6.81 (1H, d, Jꢁ10 Hz, 3-H), 6.91 (1H, d, Jꢁ10 Hz, 2-
(1H, m, 6-H), 3.75—3.81 (2H, m, 7- and 7a-H), 3.90 (2H, d, Jꢁ8 Hz, 3a-H), H), 7.24 (1H, d, Jꢁ2 Hz, ArH), 7.37—7.47 (5H, m, ArH), 7.53—7.58 (3H,
3.93 (1H, q, Jꢁ7 Hz, OCH2), 7.12—7.15 (2H, m, ArH), 7.23—7.38 (6H, m, m, ArH), 7.64 (2H, m, ArH), 8.04 (1H, d, Jꢁ2 Hz, ArH); 13C-NMR
ArH), 7.42—7.64 (5H, m, ArH), 7.85—7.87 (2H, m, ArH); 13C-NMR (100 MHz, CDCl3) 124.77 (d), 127.00 (s), 128.85 (dꢃ2), 129.03 (s), 129.18
(100 MHz, CDCl3) d: 15.35 (q), 25.19 (t), 42.89 (d), 43.44 (d), 45.96 (d), (dꢃ2), 129.50 (s), 130.30 (d), 130.45 (dꢃ2), 132.62 (s), 133.69 (d), 135.03
64.53 (t), 101.07 (s), 126.35 (dꢃ2), 127.37 (d), 128.18 (dꢃ2), 128.70 (d), (dꢃ2), 136.43 (s), 138.07 (d), 139.11 (d), 141.81 (s), 148.96 (s), 183.60 (s),
129.10 (dꢃ2), 129.15 (dꢃ2), 129.21 (dꢃ2), 129.29 (d), 130.53 (s), 131.60 184.24 (s), 196.28 (s); HR-MS Calcd for C23H14O3S : 370.0663, found: m/z
(s), 133.06 (d), 133.45 (d), 136.84 (s), 156.01 (s), 173.90 (s), 174.61 (s), 370.0648.
199.21 (s); MS m/z 531 (Mꢀ). Anal. Calcd for C29H25NO4Se: C, 65.66; H,
Reaction of 4 with DMAD A toluene (2.00 ml) solution of 4 (0.15 g,
4.75; N, 2.64. Found: C, 65.11; H, 4.76; N, 2.38.
0.48 mmol) and DMAD (0.41 g, 2.90 mmol) was refluxed under an Ar at-
Hydrolysis of 5 with Hydrochloric Acid 10%HCl–H2O (1.00 ml) was mosphere for 18 h. The work-up procedure provided dimethyl 3-benzoyl-5-
added dropwise to an EtOH (1.00 ml) solution of 5 (66 mg, 0.12 mmol). The
mixture was refluxed for 3.5 h. The mixture was poured into water (50 ml).
The work-up procedure gave 6-benzoyl-2-phenyl-3a,4,6,7,7a-pentahydro-
ethoxyphtalate (15)11) (82 mg, 50%) as a yellow oil.
Reaction of 4 with Benzoquinone A toluene (2.00 ml) solution of 4
(0.10 g, 0.32 mmol) and benzoquinone (0.24 g, 2.25 mmol) was refluxed
1H-isoindole-1,3,5(2H)-trione (7) (32 mg, 64%) as a yellow oil. IR (film, under an Ar atmosphere for 15 h. The work-up procedure afforded 5-ben-
cmꢂ1) 1710 (CO); 1H-NMR (400 MHz, CDCl3) d: 2.78 (1H, dd, Jꢁ7, 19 Hz,
4-H), 2.84—2.97 (3H, m, 6-CH2, 4-H), 3.47—3.56 (2H, m, 7a-H, 3a-H),
zoyl-7-ethoxynaphthoquinone (16)11) (54 mg, 41%) as purple prisms.
X-Ray Study of 7-Benzoyl-5-ethoxy-2-phenyl-4-(phenylselenenyl)-
4.64—4.68 (1H, m, 7-H), 7.34 (1H, dd, Jꢁ1, 8 Hz, ArH), 7.38—7.44 (3H, 3a,4,5,7a-tetrahydro-1H-isoindole-1,3(2H)-dione (5) A colorless prism
m, ArH), 7.46—7.51 (3H, m, ArH), 7.59—7.64 (1H, m, ArH), 7.86—7.91 was mounted on a glass fibre and transferred to the diffractometer.
(2H, m, ArH); 13C-NMR (100 MHz, CDCl3) d: 37.08 (d), 37.61 (t), 40.28
Crystal data for 5: C29H25O4NSe Mꢁ530.48, monoclinic, aꢁ15.328(4) Å,
(d), 40.99 (t), 42.11 (d), 126.93 (dꢃ2), 128.88 (dꢃ2), 129.06 (d), 129.30 bꢁ9.885(2) Å, cꢁ16.959(2) Å, bꢁ110.14(1)°, Vꢁ2415.5(8) Å3, Tꢁ296 K,
(dꢃ2), 129.47 (dꢃ2), 132.15 (s), 134.46 (d), 134.68 (s), 176.53 (s), 177.22 space group P21/n, Zꢁ4, m(MoKa)ꢁ1.593 mmꢂ1, DCꢁ1.460 mg mꢂ3. 6072
(s), 200.93 (s), 205.53 (s); HR-MS. Calcd for C21H17NO4: 347.1158, found reflections collected (Rigaku AFC5R diffractometer) of which 5862 were
m/z 347.1123.
unique (Rintꢁ0.077) and 2142 were observed [Iꢄ3.00s(I)]. Solved by the
Reaction of 2 with N-Methylmaleimide A benzene (3.00 ml) solution
DIRDIF program system (ORIENT)15) and refined by full-matrix least
of 2 (0.20 g, 0.56 mmol) and N-methylmaleimide (0.37 g, 3.4 mmol) was squares (teXsan) on F of all unique data to Rꢁ0.044, Rwꢁ0.047. CCDC
heated 36 h under an Ar atmosphere. The work-up procedure provided 7-
benzoyl-5-ethoxy-2-methyl-4-(phenylselenenyl)-3a,4,5,7a-tetrahydro-1H-
isoindole-1,3(2H)-dione (8) (140 mg, 57%) as white prisms. mp 158—
162 °C (dec.); IR (KBr, cmꢂ1) 1780, 1700 (CO), 1220, 1100 (ether); 1H-
NMR (400 MHz, CDCl3) d: 1.15 (3H, t, Jꢁ7 Hz, Me), 2.53 (1H, ddd, Jꢁ2,
11, 18 Hz, 6-H), 2.74 (1H, dd, Jꢁ4, 18 Hz, 6-H), 2.83 (3H, s, N-Me), 3.62
(1H, ddd, Jꢁ1, 5, 9 Hz, 7a-H), 3.70 (1H, td, Jꢁ5, 11 Hz, 7-H), 3.77 (1H, dd,
Jꢁ2, 9 Hz, 3a-H), 3.90 (2H, q, Jꢁ7 Hz, OCH2), 7.22—7.30 (3H, m, ArH),
7.44—7.58 (5H, m, ArH), 7.85—7.88 (2H, m, ArH); 13C-NMR (100 MHz,
CDCl3) d: 15.23 (q), 24.73 (t), 24.93 (q), 42.89 (d), 44.01 (d), 45.72 (d),
64.22 (t), 100.33 (s), 127.13 (d), 128.01 (dꢃ2), 128.95 (dꢃ2), 129.05
(dꢃ2), 130.40 (s), 132.90 (d), 132.99 (dꢃ2), 136.74 (s), 155.80 (s), 175.13
(s), 175.49 (s), 199.20 (s); MS m/z 469 (Mꢀ). Anal. Calcd for C24H23NO4Se:
186627.
References
1) Petrzilka M., Grayson J. I., Synthesis, 1981, 753—786 (1981).
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