6
I. E. ISMAILOV ET AL.
þ
calcd for C H O PS: C 56.15, H 4.71. Found: C 56.20, (ESI): m/z calcd for C H Cl O P [M þ H] 489.3269,
1
9
19
6
25 24
2 4
H 4.77.
found 489.3288. Anal. calcd for C H Cl O P: C 61.36, H
25 23 2 4
4
.74. Found: C 61.30, H 4.79.
5
-Ethoxycarbonyl-2,2,5-triphenyl-4-phenylselenenyl-3-(tet-
rahydro-2H-pyran-2-yloxymethyl)-2,5-dihydro-1,2-oxaphos- 4-Chloro-5-(diphenylphosphinoyl)-5-hydroxymethyl-3-phe-
phol-2-ium chloride 7a nyl-5H-furan-2-one 8b
Colorless oil, yield: 52%. Eluent for TLC: ethyl acetate:hex- Orange oil, yield: 27%. Eluent for TLC: ethyl acetate:hexane
ꢀ
1
ꢀ1
ane ¼ 6:1, R 0.44; IR (neat, cm ): 1121 (C-O-C), 1441, ¼ 1:3, R 0.59; IR (neat, cm ): 1119 (C-O-C), 1180 (P ¼ O),
f
f
1
1
490 (Ph), 1582 (C ¼ C), 1726 (C ¼ O).
H
NMR 1441, 1492 (Ph), 1621 (C ¼ C), 1745 (C ¼ O), 3393 (OH).
1
(600.1 MHz): d 1.25 (t, J ¼ 6.8 Hz, 3 H, MeCH O), 1.44–1.69
H NMR (600.1 MHz): d 4.51–4.74 (m, 2 H, CH ), 6.24 (s,
2
2
13
(m, 6 H, OTHP), 3.57–3.72 (m, 2 H, OTHP), 4.16 (q, 1 H, OH), 7.41–7.99 (m, 15 H, 3Ph). C NMR (150.9 MHz):
J ¼ 6.8 Hz, 2 H, MeCH O), 4.55–4.71 (m, 2 H, CH ), d 67.1 (J ¼ 5.9 Hz, CH ), 101.0 (J ¼ 126.7 Hz, C), 126.9 (CH),
2
2
2
13
4
.68–4.79 (m, 1 H, OTHP), 6.79–8.37 (m, 20 H, 4Ph).
C
127.3 (CH), 128.9 (J ¼ 7.9 Hz, CH), 129.6 (CH), 130.6
NMR (150.9 MHz): d 14.1 (CH ), 19.7 (CH ), 26.2 (CH ), (J ¼ 9.8 Hz, CH), 130.9 (J ¼ 4.7 Hz, CH), 131.4 (J ¼ 4.6 Hz,
3
2
2
3
9
1.4 (CH ), 61.4 (CH ), 62.8 (CH ), 63.7 (J ¼ 5.7 Hz, CH ), C), 132.1 (J ¼ 89.8 Hz, C), 145.2 (J ¼ 7.8 Hz, C), 158.3
2
2
2
2
31
8.5 (J ¼ 5.0 Hz, CH), 99.4 (J ¼ 9.8 Hz, C), 127.4 (J ¼ 7.7 Hz, (J ¼ 39.4 Hz, C), 168.7 (J ¼ 7.9 Hz, C).
P
NMR
CH), 127.8 (CH), 128.1 (CH), 128.4 (J ¼ 4.5 Hz, C), 128.9 (242.9 MHz): d 16.7. Anal. calcd for C H ClO P: C 65.03,
P
23 18
4
(
(
(
CH), 129.1 (J ¼ 50.2 Hz, C), 130.4 (J ¼ 9.7 Hz, CH), 130.7 H 4.27. Found: C 65.07, H 4.33.
J ¼ 5.1 Hz, CH), 131.2 (J ¼ 75.0 Hz, C), 131.3 (CH), 131.4
J ¼ 49.4 Hz, J ¼ 5.1 Hz, C), 138.7 (CH), 140.3 (J ¼ 7.9 Hz,
3
1
General procedure for silver-catalyzed cycloisomerization
of the 4-phosphorylated 5-hydroxypenta-2,3-dienoates 3
and 4
Method A: Silver perchlorate (0.15 mmol) was added to a
solution of 4-phosphorylated 5-hydroxypenta-2,3-dienoate 3
CH), 176.4 (J ¼ 7.9 Hz, C), 182.7 (J ¼ 14.6 Hz, C). P NMR
(
6
242.9 MHz): d 83.5. Anal. calcd for C H ClO PSe: C
P
36 36
5
2.30, H 5.23. Found: C 62.24, H 5.19.
5
-(Diphenylphosphinoyl)-3-phenyl-4-phenylselenenyl-5-(tet- or 4 (3.0 mmol) in dry dichloromethane (10 mL) The mix-
.
rahydro-2H-pyran-2-yloxymethyl)-5H-furan-2-one 8a
Orange oil, yield: 28%. Eluent for TLC: ethyl acetate:hexane (for 9a) and 9 h (for 9 b). Saturated sodium chloride solu-
ture was stirred at room temperature and in the dark for 7 h
ꢀ
1
¼
6:1, R 0.66; IR (neat, cm ): 1115 (C-O-C), 1177 (P ¼ O), tion was added to precipitate the silver ions. The product
f
1
1
437, 1489 (Ph), 1624 (C ¼ C), 1750 (C ¼ O). H NMR was extracted by chloroform. The organic layer was dried
(
600.1 MHz): d 1.41–1.66 (m, 6 H, OTHP), 3.62–3.73 (m, over anhydrous sodium sulfate. After evaporation of the
2
H, OTHP), 4.44–4.65 (m, 2 H, CH ), 4.60–4.71 (m, 1 H, solvent, the residue was chromatographed on a column with
2
13
OTHP), 7.30–7.84 (m, 20 H, 4Ph). C NMR (150.9 MHz): d a mixture of ethyl acetate and hexane as an eluent to give
9.7 (CH ), 26.3 (CH ), 31.7 (CH ), 63.0 (CH ), 72.4 the pure products 9 as oils.
1
2
2
2
2
(
J ¼ 5.8 Hz, CH ), 97.2 (J ¼ 4.9 Hz, CH), 100.5 (J ¼ 126.7 Hz,
Method B: The 4-phosphorylated 5-hydroxypenta-2,3-
2
C), 127.4 (CH), 128.2 (CH), 128.6 (J ¼ 7.8 Hz, CH), 128.8 dienoate 3 or 4 (3.0 mmol) is dissolved in 40:60 water/acet-
(
(
J ¼ 9.9 Hz, CH), 129.0 (CH), 129.4 (J ¼ 84.8 Hz, C), 129.8 one (10 mL) containing calcium carbonate (1 mmol) and sil-
J ¼ 49.7 Hz, J ¼ 5.0 Hz, C), 130.1 (CH), 130.9 (J ¼ 9.7 Hz, ver nitrate (0.3 mmol). The mixture was stirred at room
CH), 131.8 (J ¼ 5.0 Hz, CH), 132.8 (J ¼ 5.2 Hz, C), 138.4 temperature and in the dark for 12 h (for 9a) and 15 h (for
(
(
CH), 142.4 (J ¼ 7.7 Hz, C), 171.1 (J ¼ 7.6 Hz, C), 179.4 9a). The product is taken up in diethyl ether and the ether
31
J ¼ 15.0 Hz, C). P NMR (242.9 MHz): d 15.1. Anal. calcd solution is washed with saturated sodium chloride solution.
P
for C H O PSe: C 64.87, H 4.96. Found: C 64.93, H 5.00.
The organic layer was dried over anhydrous magnesium sul-
fate. After evaporation of the solvent, the residue was chro-
matographed on a column with a mixture of ethyl acetate
and hexane as an eluent to give the pure products 9 as oils,
which had the following properties:
3
4
31 5
4
2
-Chloro-5-ethoxycarbonyl-3-hydroxymethyl-2,2,5-triphenyl-
,5-dihydro-1,2-oxaphosphol-2-ium chloride 7b
Colorless oil, yield: 50%. Eluent for TLC: ethyl acetate:hex-
ꢀ
1
ane ¼ 1:3, R 0.40; IR (neat, cm ): 1439, 1487 (Ph), 1580
f
1
(
1
C ¼ C), 1723 (C ¼ O), 3397 (OH). H NMR (600.1 MHz): d Ethyl 4-(dimethylphosphoryl)-2-phenyl-2,5-dihydrofuran-2-
.26 (t, J ¼ 6.7 Hz, 3 H, MeCH O), 4.15 (q, J ¼ 6.7 Hz, 2 H, carboxylate 9a
2
MeCH O), 5.11 (d, J ¼ 16.7 Hz, 2 H, CH ), 5.41 (s, 1 H, Yellow oil, yield: 90% (Method A), 68% (Method B). Eluent
2
2
13
OH), 7.01–8.44 (m, 15 H, 3Ph). C NMR (150.9 MHz): d for TLC: ethyl acetate:hexane ¼ 1:3, R 0.54; IR (neat,
f
ꢀ
1
1
(
4.2 (CH ), 60.2 (J ¼ 6.1 Hz, CH ), 62.3 (CH ), 97.4 cm ): 1121 (C-O-C), 1269 (P ¼ O), 1439, 1492 (Ph), 1622
3
2
2
1
J ¼ 10.1 Hz, C), 123.7 (J ¼ 8.1 Hz, CH), 123.9 (J ¼ 74.9 Hz, (C ¼ C), 1723 (C ¼ O). H NMR (600.1 MHz): d 1.37 (t,
C), 129.3 (J ¼ 5.0 Hz, CH), 129.6 (CH), 130.5 (J ¼ 45.8 Hz, J ¼ 6.8 Hz, 3 H, MeCH O), 3.64 (d, J ¼ 10.7 Hz, 6 H, 2MeO),
2
C), 130.8 (J ¼ 4.6 Hz, CH), 131.1 (CH), 133.8 (J ¼ 9.8 Hz, 4.26 (q, J ¼ 6.8 Hz, 2 H, MeCH O), 4.78 (dd, J ¼ 7.8 Hz,
2
CH), 136.1 J ¼ 7.8 Hz, C), 166.3 (J ¼ 39.8 Hz, C), 168.4 J ¼ 1.7 Hz, 2 H, CH ), 7.23 (dt, J ¼ 10.7 Hz, J ¼ 1.5 Hz, 1 H,
2
3
1
13
(
J ¼ 7.9 Hz, C). P NMR (242.9 MHz): dP 80.8. HRMS ¼CH), 7.27–7.91 (m, 5 H, Ph). C NMR (150.9 MHz): d