8398 J . Org. Chem., Vol. 64, No. 22, 1999
Notes
(tricyclohexylphosphine)benzylidene ruthenium(IV) dichloride (7
mg, 8.5 µmol, 4 mol %) was added to a stirred solution of 7 (100
mg, 0.2 mmol) in toluene (5 mL) under an atmosphere of argon.
4.58 (ABq, J 12.3 Hz, 2H), 4.75 and 4.92 (ABq, J 11.1 Hz, 2H),
7.12-7.36 (m, 15H). 13C NMR (75 MHz, CDCl3) δ 35.8, 50.1, 54.3,
69.1, 71.5, 73.5, 75.0, 75.1, 75.7, 77.3, 78.9, 85.2, 89.8, 127.5,
127.6, 127.7, 127.7, 127.8, 127.9, 128.3, 137.9, 138.0, 138.8.
HRMS m/e calcd for C31H34O6Na (M + Na+): 525.225, found
525.226.
The reaction color changed from
a pink-purple to a clear
brownish solution. The reaction was left to stir overnight at room
temperature and then filtered through a pad of Celite and
concentrated in vacuo. Purification by flash chromatography
(10%EtOAc/petroleum ether) gave 1 as a colorless oil (77 mg,
(2R,3R,4S,4a S,7R,8R,9a S)-3,4-Bis(ben zyloxy)-2-(ben zyl-
oxymethyl)-7,8-dihydroxy-2,3,4,4a,7,8,9,9a-octahydro-6H-pyrano-
[3,2-b]oxep in (10) a n d (2R,3R,4S,4a S,7S,8S,9a S)-3,4-Bis-
(b e n zyloxy)-2-(b e n zyloxym e t h yl)-7,8-d ih yd r oxy-2,3,4,-
4a ,7,8,9,9a -octa h yd r o-6H-p yr a n o[3,2-b]oxep in (11). To a
solution of the epoxide 8 (42 mg, 0.084 mmol) in THF (0.7 mL)
was added in portions 10% aqueous H2SO4 (3.5 mL), and the
reaction mixture was stirred overnight at room temperature.
Sodium hydroxide (1 pellet) was added to the reaction mixture
which was then washed with saturated aqueous sodium chloride
solution (10 mL) and the aqueous phase extracted with ethyl
acetate (3 × 10 mL). The combined organic extracts were dried
(CaO), filtered, and concentrated in vacuo to give a solid (23 mg).
Separation of the two isomers by HPLC provided pure samples
of each of the isomers. 10: Low Rf isomer. mp 118.5-120 °C.
[R]33D-4.9 (c 0.41, CHCl3). 1H NMR (400 MHz, CDCl3) δ 1.62
(bs, 2H, 1.84 (dt, J 13.5, 10.8 Hz, 1H), 2.34 (ddd, J 13.5, 4.2, 2.4
Hz, 1H), 3.10-3.15 (m, 1H), 3.30 (ddd, J 10.8, 9.7, 4.2 Hz, 1H),
3.42-3.47 (m, 1H), 3.49-3.56 (m, 2H), 3.63 (dd, J 10.8, 4.5 Hz,
1H), 3.70 (dd, J 10.8, 2.0 Hz, 1H), 3.73 (dd, J 8.3, 5.8, 4.6 Hz,
1H), 3.86 (ddd, J 10.8, 8.3, 2.4, 1H), 3.90 (dd, J 13.2, 4.6 Hz,
1H), 4.01 (dd, J 13.2, 5.8 Hz, 1H), 4.49, 4.82 (ABq, J 10.7 Hz,
2H), 4.52, 4.59 (ABq, J 12.1 Hz, 2H), 4.77, 4.90 (ABq, J 11.2
Hz, 2H), 6.99-7.36 (m, 15H). 13C NMR (75 MHz, CDCl3) δ 39.3,
69.0, 70.7, 73.5, 74.0, 75.1, 75.5, 75.6, 76.1, 77.6, 79.0, 85.2, 85.9,
127.6, 127.6, 127.7, 127.8, 127.9, 128.3, 137.9, 138.0, 138.7. IR
(CHCl3) 3522, 3376 cm-1. HRMS calcd for (C31H36O7Na)+: m/z
543.236, found 543.236. 11: High Rf isomer. mp 100.5-102.5
81%). [R]28 +12.5 (c, 1.1, CHCl3). 1H NMR (400 MHz, CDCl3) δ
D
2.39-2.50 (m, 1H), 2.72 (ddd, J 16.2, 8.0, 4.0 Hz, 1H), 3.27 ddd
(J 10, J 9.3, J 4.0 Hz, 1H), 3.44 (dd, J 9.3, J 8.4 Hz, 1H), 3.47
(ddd, J 9.5, J 4.6, J 1.9 Hz, 1H), 3.58 (dd J 9.5, J 8.7 Hz, 1H),
3.65 (dd, J 10.6, J 4.6 Hz, 1H), 3.66 (dd, J 8.7, J 8.4 Hz, 1H),
4.00 (ddd, J 15.2, J 5.3 J 2.5 Hz, 1H), 4.30 (dd, J 15.2, J 5.9,
1H), 4.56, 4.62, (ABq, J 12.2 Hz, 2H), 4.52, 4.86 (ABq, J 10.7
Hz, 2H), 4.82, 4.98 (ABq, J 11.2 Hz, 2H), 5.82 (dddd, J 4 11.4, J
8.0, J 3 0.4, J 2.5 Hz, 1H), 5.92 (dddd, J 11.4, J 5.9, J 3.6, 3.0
Hz, 1H), 7.14-7.42 (m, 15H). 13C NMR (100 MHz, CDCl3) δ 34.6,
67.8, 69.3, 73.5, 75.0, 75.6, 76.0, 77.8, 78.4, 85.8, 88.1, 127.4,
127.5, 127.4, 127.6, 127.7, 127.9, 128.0, 128.3, 128.3, 131.5, 138.2,
138.4, 139.1. MS m/z 487.4 (M + H+), 509.4 (M + Na+), 525.3
(M + K+). IR (film) 1606 cm-1. HRMS m/e calcd for C31H34O5Na
(M + Na+): 509.230, found 509.231.
(2R,3R,4S,4a S,7R,8R,9a S)-3,4-Bis(ben zyloxy)-2-(ben zyl-
oxymethyl)-2,3,4,4a,7,8,9,9a-octahydro-6H-pyrano[3,2-b]oxepin-7,8-
ep oxid e (8) a n d (2R,3R,4S,4a S,7S,8S,9a S)-3,4-Bis(b en -
zyloxy)-2-(benzyloxymethyl)-2,3,4,4a,7,8,9,9a-octahydro-6H-pyrano-
[3,2-b]oxep in -7,8-ep oxid e (9). A solution of oxepin 1 (300 mg,
0.62 mmol) in dichloromethane (12 mL) was cooled to 0 °C and
mCPBA (500 mg, 2.47 mmol, 85% pure) was added slowly. The
reaction mixture was maintained at 0 °C, and then warmed to
ambient temperature and stirred for 2 h. Solid NaOH (1 pellet)
was then added to the reaction mixture. This mixture was
diluted with saturated aqueous NaCl (20 mL) and extracted with
ethyl acetate (3 × 20 mL). The organic extract was dried (CaO)
and the crude material purified by preparative chromatography
(ethyl acetate/light petroleum) providing the epoxides 8 and 9
(total mass of 186 mg) in 60% and 5% yields, respectively. 8:
mp 103-106 °C. [R]28D +5.6 (c 0.8, CHCl3). IR (Nujol) 1497, 1453,
°C. [R]33 +8.9 (c 0.25, CHCl3). 1H NMR (500 MHz, CDCl3) δ
D
2.17 (bs, 2H), 2.20 (t, J 6.0 Hz, 2H), 3.28-3.34 (m, 1H), 3.43
(ddd, J 9.7, 4.7, 1.9 Hz, 1H), 3.47 (dd, J 12.6, 7.7 Hz, 1H), 3.51
(dd, J 3.9, 2.0 Hz, 1H), 3.52-3.56 (m, 2H), 3.63 (dd, J 10.8, 4.7
Hz, 1H), 3.67-3.71 (m, 1H), 3.96-4.00 (m, 1H), 4.13 (dd, J 12.5,
4.6 Hz, 1H), 4.49, 4.82 (ABq, J 10.8 Hz, 2H), 4.52, 4.59 (ABq, J
12.3 Hz, 2H), 4.77, 4.90 (ABq, J 11.1 Hz, 2H), 7.13-7.36 (m,
15H). 13C NMR (125.77 MHz, CDCl3) δ 36.8, 69.3, 70.8, 72.0,
73.6, 74.3, 74.8, 75.1, 75.4, 78.0, 79.4, 84.4, 85.2, 127.7, 127.7,
127.7, 127.9, 128.4, 138.0, 138.1, 138.2. IR (CHCl3) 3487, 3175
cm-1. HRMS calcd for (C31H36O7Na)+: m/z 543.236, found
543.236.
1
1360, 1105, 1073, 1028, 912, 749, 697, 668 cm-1. H NMR (300
MHz, CDCl3) δ 2.06 (dd, J 15.3, 10.9 Hz, 1H), 2.83 (dt, J 15.3,
4.6 Hz, 1H), 2.96 (dd, J 9.2, 8.4 Hz, 1H), 3.04 (dd, J 4.2, 3.0 Hz,
1H), 3.22 (t, J 4.6 Hz, 1H), 3.36-3.45 (m, 2H), 3.50 (dd, J 9.4,
9.1 Hz, 1H), 3.59 (dd, J 9.0, 8.4 Hz, 1H), 3.63 (dd, J 10.8, 4.5
Hz, 1H), 3.69 (dd, J 10.8, 2.0 Hz, 1H), 3.79 (d, J 14.3 Hz, 1H),
4.41 (dd, J 14.3, 3.1 Hz, 1H), 4.50 and 4.81 (ABq, J 10.8 Hz,
2H), 4.52 and 4.59 (ABq, J 12.2 Hz, 2H), 4.79 and 4.90 (ABq, J
11.2 Hz, 2H), 7.12-7.37 (m, 15H, Ph). 13C NMR (75 MHz, CDCl3)
δ 33.7, 52.6, 55.5, 66.3, 69.0, 73.5, 75.0, 75.2, 75.8, 77.2, 78.1,
85.6, 86.9, 127.4, 127.5, 127.5, 127.7, 127.7, 127.8, 128.2, 137.9,
138.1, 138.9. HRMS m/e calcd for C31H34O6Na (M + Na+):
525.225, found 525.222. 9: oil. [R]S(28,D) +12.7 (c 0.45, CHCl3).
1H NMR (500 MHz, CDCl3) δ 1.83 (ddd, J 14.0, 11.9, 7.1 Hz,
1H), 2.64 (ddd, J 14.0, 7.0, 2.0 Hz, 1H), 3.12-3.15 (m, 1H), 3.21-
3.27 (m, 3H), 3.30-3.34 (m, 1H), 3.44-3.46 (m, 1H), 3.49 (dd, J
9.8, 8.6 Hz, 1H), 3.57-3.62 (m, 2H), 3.68 (app d, J 10.5 Hz, 1H),
4.47-4.49 (m, 1H), 4.47 and 4.81 (ABq, J 10.8 Hz, 2H), 4.53 and
Ack n ow led gm en t. S.G. is grateful to the Australian
Government for an Australian Postgraduate Research
Award. We thank Dr. G. D. Fallon for determining the
X-ray crystal structure of 8.
Su p p or t in g In for m a t ion Ava ila b le: 1H and 13C NMR
spectra of all new compounds. This material is available free
J O990389C