1514
M.T.S. Shafawati et al. / Tetrahedron 69 (2013) 1509e1515
J¼7.1 Hz), 2.59 (br s, 1H), 2.37e2.34 (m, 4H), 2.27 (s, 2H), 2.07 (s,
3H),1.01 (s, 6H). 13C NMR
198.1,170.7, 140.0, 136.7, 101.0, 86.7, 84.0,
4.15. 2-Diethoxyphosphinyl-14,14-dimethyl-8-phenylsulfonyl-
tricyclo[9.4.0.03,7]pentadeca-1(11),2,6-triene-5,12-dione (25)
d
74.7, 52.7, 51.42, 51.35, 44.8, 33.3, 27.9, 26.7, 20.8, 17.9. DARTMS m/z
303 (Mþþ1, 100); DARTHRMS calcd for C18H23O4 303.1596, found
303.1587.
Compound 25 was brown crystals; mp 169e171 ꢀC (CH2Cl2);
IR 1708, 1670, 1323, 1310, 1263, 1238, 1153, 1024 cmꢁ1 1H NMR
;
7.83e7.81 (m, 2H), 7.70e7.66 (t, 1H, J¼7.3 Hz), 7.56e7.53 (m, 2H),
7.27 (s, 1H), 4.16e4.02 (m, 5H), 3.86 (dd, 1H, J¼22.0, 2.7 Hz), 3.25
(dd, 1H, J¼22.0, 3.2 Hz), 3.22 (dd, 1H, J¼18.3, 4.1 Hz), 2.96e2.92
(m, 1H), 2.30 (d, 1H, J¼15.6 Hz), 2.20e2.00 (m, 5H), 1.35 (t, 3H,
J¼6.9 Hz), 1.31 (t, 3H, J¼6.9 Hz), 1.10 (s, 3H), 0.86 (s, 3H). 13C NMR
4.13. Diethyl 1-[2-(5-hydroxypent-3-ynyl)-5,5-dimethyl-3-
oxocyclohex-1-enyl]propa-1,2-dienylphosphonate (23)
To a solution of 21a (39 mg, 0.13 mmol) in THF (1.5 mL) were
added Et3N (0.050 mL, 0.26 mmol) and diethyl chlorophosphite
(30 mL, 0.20 mmol) at ꢁ78 ꢀC. After stirring for 30 min at the same
temperature, the reaction mixture was warmed to room tempera-
ture and then heated at reflux for 9 h. The reaction mixture was
quenched by addition of saturated aqueous NaHCO3, extracted with
AcOEt. The extract was washed with water and brine, dried, and
concentrated to dryness. The residue was chromatographed with
DCM/AcOEt (1:1) to afford the phosphonyl allene (22 mg, 40%) as
d
201.5, 196.8, 160.7 (d, J¼28.9 Hz), 150.7 (d, J¼7.2 Hz), 150.6 (d,
J¼11.6 Hz), 138.9, 137.3, 134.5, 134.0 (d, J¼14.5 Hz), 129.4, 128.8,
127.8 (d, J¼176.3 Hz), 63.3, 62.7 (t, J¼4.3 Hz), 50.8, 44.0, 41.4 (d,
J¼4.3 Hz), 32.9, 29.8 (d, J¼8.7 Hz), 27.2, 22.3, 16.4 (d, J¼5.8 Hz),
16.3 (d, J¼8.7 Hz), 14.1 (d, J¼11.6 Hz); DARTMS m/z 533 (Mþþ1,
27); DARTHRMS calcd for C27H34O7PS 533.1763, found 533.1755.
Regiochemistry of 25 was determined by HMQC and HMBC.
a yellow oil. IR 1960, 1931, 1738, 1668, 1265, 1024 cmꢁ1
;
1H NMR
Acknowledgements
d
5.14 (s, 1H), 5.11 (s, 1H), 4.61 (s, 2H), 4.20e4.07 (m, 4H), 2.56 (t, 2H,
J¼7.8 Hz), 2.47e2.46 (m, 2H), 2.31e2.26 (m, 4H), 2.06 (s, 3H),1.32 (t,
6H, J¼7.0 Hz),1.01 (s, 6H). 13C NMR
210.2 (d, J¼3.8 Hz),198.7,170.3,
d
This work was supported in part by a Grant-in Aid for Scientific
Research from the Ministry of Education, Culture, Sports, Science
and Technology, Japan, for which we are thankful. M.T.S.S. thanks
the Ministry of Higher Education, Malaysia, for the postgraduate
scholarship.
147.2 (d, J¼3.8 Hz), 135.7 (d, J¼8.6 Hz), 96.7, 94.8, 87.1, 74.3, 63.0 (d,
J¼6.7 Hz), 52.8, 51.3, 45.0, 33.1, 27.9, 26.3 (d, J¼1.9 Hz), 20.8, 18.1 (d,
J¼1.9 Hz), 16.2 (d, J¼6.2 Hz). DARTMS m/z 423 (Mþþ1, 100);
DARTHRMS calcd for C22H32O6P 423.1937, found 423.1940. To a so-
lution of the phosphonyl allene (16 mg, 4.0ꢂ10ꢁ2 mmol) in MeOH
(0.5 mL) was added K2CO3 (7 mg, 0.04 mmol). After stirring for
5 min, the mixture was quenched with water, extracted with AcOEt.
The extract was washed with brine, dried, and concentrated to
dryness. The residue was chromatographed with hexane/AcOEt
(1:2) to afford 23 (9.5 mg, 62%) as a colorless oil. IR 3597, 3398,
References and notes
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2222, 1960, 1929, 1711, 1666, 1265, 1024 cmꢁ1. 1H NMR
d 5.11 (s, 1H),
5.07 (s, 1H), 4.18e4.08 (m, 6H), 2.53 (t, 2H, J¼7.3 Hz), 2.46e2.45 (m,
2H), 2.35e2.31 (m, 2H), 2.26 (s, 2H), 1.32 (t, 6H, J¼7.8 Hz), 1.02 (s,
6H). 13C NMR
d
210.2 (d, J¼2.9 Hz), 198.9, 147.4 (d, J¼3.8 Hz), 135.6
(d, J¼8.6 Hz), 96.6, 94.7, 84.9, 79.6, 63.0 (d, J¼6.7 Hz), 51.4, 50.9,
44.9, 33.0, 27.8, 26.0 (d, J¼1.9 Hz), 17.8 (d, J¼2.9 Hz), 16.1 (d,
J¼6.7 Hz). DARTMS m/z 381 (Mþþ1, 100); DARTHRMS calcd for
C20H30O5P 381.1831, found 381.1829.
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3,4-dienyl)cyclohex-1-enyl]propa-1,2-dienylphosphonate (24)
~
ꢁ
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1265, 1145, 1024 cmꢁ1 1H NMR
. d 7.85e7.84 (m, 2H), 7.58 (t, 1H,
J¼7.6 Hz), 7.50 (m, 2H), 5.36 (t, 2H, J¼3.4 Hz), 5.05 (s, 1H), 5.03 (s,
1H), 4.15e4.05 (m, 4H), 2.45e2.41 (m, 4H), 2.25e2.22 (m, 4H), 1.32
(t, 6H, J¼7.0 Hz), 1.01 (s, 6H). 13C NMR 209.9, 207.7, 198.6, 147.5 (d,
J¼2.9 Hz), 140.2, 135.7 (d, J¼10.1 Hz), 133.3, 129.0, 127.9, 113.2, 96.0,
94.7, 84.5, 62.9 (d, J¼7.2 Hz), 51.3, 44.8, 33.1, 29.5, 27.8, 25.5 (d,
J¼2.9 Hz), 25.4, 16.2 (d, J¼7.2 Hz). DARTMS m/z 505 (Mþþ1, 100);
DARTHRMS calcd for C26H34O6PS 505.1814, found 505.1815.
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