K. Tsubaki et al. / Tetrahedron 58 12002) 5611±5617
5615
palladium on carbon 6500 mg) in 1,4-dioxane 6200 ml) and
ethanol 6100 ml) was stirred at 608C for 4 h. Ammonium
formate 66.0g, 95 mmol) and 10% palladium on carbon
6500 mg) were further added to the reaction mixture. The
reaction mixture was stirred for another 4 h at 608C. After
®ltration, the ®ltrate was evaporated and the precipitate was
triturated with water and ethanol 61/1) to afford the desired
diol 6 as white powder 66.18 g, 94% yield). Mp 184±1868C;
under reduced pressure, and the residue was poured into
ethyl acetate and aqueous hydrochloric acid. The organic
layer was separated and washed with water 6twice) and then
dried over magnesium sulfate and evaporated in vacuo to
give the tetramethylether in quantitative yield, which was
directly used for the next step without further puri®cation.
1H NMR 6200 MHz, CDCl3) d 2.41 6s, 3H), 3.47 6s, 3H),
3.64 6s, 3H), 3.706s, 3H), 3.73 6s, 3H), 5.35 6s, 2H), 7.13±
7.64 616H), 7.74±7.92 63H). A solution of the crude tetra-
methylether 60.87 g, 1.3 mmol) and 1N sodium hydroxide
63.9 ml, 3.9 mol) in THF 650ml) was re¯uxed for 8 h. The
solvent was evaporated under reduced pressure and the
residue was partitioned between ethyl acetate and aqueous
hydrochloric acid. The organic layer was washed with brine
6twice), dried over magnesium sulfate and evaporated to
give the alcohol 6770mg, 94%). 1H NMR 6200 MHz,
CDCl3) d 3.46 6s, 3H), 3.64 6s, 3H), 3.71 6s, 3H), 3.73 6s,
3H), 5.36 6s, 2H), 7.14±7.64 616H), 7.76±7.9063H), 7.92 6s,
3H). A suspension of palladium on carbon 610%, 350 mg) in
EtOH 610ml) was added to the solution of the alcohol
6500 mg) in THF 615 ml). Ammonium formate 61.4 g,
22 mmol) was added the mixture and stirred for 608C for
4 h. After the catalyst was ®ltered off, the ®ltrate was evapo-
rated under reduced pressure, the residue was poured into
ethyl acetate and aqueous hydrochloric acid. The organic
layer was separated and washed with brine 6twice) and then
dried over magnesium sulfate and evaporated in vacuo. The
residue was puri®ed by column chromatography 6SiO2,
dichloromethane/n-hexane/ethyl acetate5/4/1) to afford 9
as colorless powder 6435 mg). Mp 264±2668C 6triturated
with n-hexane/ethyl acetate); IR 6KBr) 3480, 1506,
1
IR 6KBr) 3603, 3429, 3163, 1618, 1598 cm21; H NMR
6200 MHz, CDCl3) d 3.33 6s, 6H), 6.14 6brs, 2H, ±OH),
7.12±7.14 64H), 7.33±7.42 62H), 7.49 6s, 2H), 7.77 6d,
J8.2 Hz, 2H); HRMS Calcd for C22H18O4: 346.1205.
Found: 346.1206; Anal. Calcd for C22H18O4: C, 76.29; H,
5.24. Found: C, 76.00; H, 5.17.
3.1.2. Monoacetate 7. To a solution of 6 657.0g, 0.16 mol)
and triethylamine 633.0ml, 0.24 mol) in DMF 610ml) and
THF 6800 ml), acetyl chloride 613.5 ml, 0.19 mol) was
added dropwise at 08C for 3.5 h. Acetyl chloride 61.1 ml,
16 mmol) was further added to the reaction mixture. The
mixture was stirred for another 1 h. The reaction mixture
was evaporated and the residue was partitioned between
water and ethyl acetate. The organic layer was separated,
washed successively with hydrochloric acid, water 6two
times), and brine, dried over magnesium sulfate, and
evaporated in vacuo. The residue was puri®ed by column
chromatography 6SiO2, n-hexane/ethyl acetate5/1±3/1) to
afford 7 as a pale yellow solid 619.8 g, 32% yield). Mp
184±1868C 6triturated with n-hexane/ethyl acetate); IR
6KBr) 3284, 1725, 1599 cm21
;
1H NMR 6200 MHz,
CDCl3) d 2.39 6s, 3H), 3.38 6s, 3H), 3.39 6s, 3H), 6.19
6brs, 1H, ±OH), 7.0±8.0 610H); HRMS Calcd for
C24H20O5: 388.1311. Found: 388.1305; Anal. Calcd for
C24H20O5: C, 74.21; H, 5.19. Found: C, 74.33; H, 5.17.
1
1465 cm21; H NMR 6200 MHz, CDCl3) d 3.47 6s, 6H),
3.72 6s, 6H), 6.16 6s, 2H), 7.16±7.47 610H), 7.51 6s, 2H),
7.82 6d, J8.1 Hz, 2H); HRMS Calcd for C34H28O6:
532.1886. Found: 532.1875; Anal. Calcd for C34H28O6: C,
76.68; H, 5.30. Found: C, 76.66; H, 5.27.
3.1.3. Ternaphthalene 8. To a suspension of CuCl2 61.4 g,
10mmol) in methanol 65.0ml), a-phenylethylamine
61.8 ml, 14 mmol) was added under nitrogen atmosphere
under ice bath cooling. After 20min, a solution of 7
6200 mg, 0.52 mmol) and 5 61.2 g, 5.2 mmol) in dichloro-
methane 620ml) was added and the reaction mixture was
stirred for 18 h at room temperature. Conc. hydrochloric
acid was added to the reaction mixture and extracted with
ethyl acetate. The organic layer was washed with water and
brine, dried over magnesium sulfate and evaporated to give
residue. The residue was puri®ed by column chroma-
tography 6SiO2, dichloromethane/n-hexane/ethyl acetate
5/4/1) to afford 8 as colorless powder 639 mg, 24% yield)
as well as 6S,S) and 6R,R)-8 642 mg, 25% yield) and
binaphthyl derivative 6700 mg). Mp 151±1538C 6triturated
with n-hexane/ethyl acetate); IR 6KBr) 3523, 1762,
3.1.5. Ditri¯ate 10. To a solution of 9 61.50g, 2.8 mmol)
and diisopropylethylamine 62.4 ml, 14 mmol) in dichloro-
methane 650ml) was dropwise added tri¯uoromethane-
sulfonic anhydride 61.9 ml, 11 mmol) under ice-bath
cooling. The reaction mixture was allowed to be back to
room temperature and stirred for 1 h. Further, diisopropyl-
ethylamine 61.2 ml, 7 mmol) and tri¯uoromethanesulfonic
anhydride 61.0ml, 6 mmol) were successively added to the
solution at room temperature for 1 h. The reaction mixture
was evaporated under reduced pressure, and the residue was
poured into ethyl acetate and aqueous hydrochloric acid.
The organic layer was separated and washed with 2%
aqueous sodium hydroxide, aqueous hydrochloric acid,
water and then dried over magnesium sulfate and evapo-
rated in vacuo. The residue was puri®ed by column
chromatography 6SiO2, dichloromethane/n-hexane1/1) to
afford 10 as a white powder 61.77 g, 79% yield). Mp 236±
2388C 6triturated with n-hexane/ethyl acetate); IR 6KBr)
1
1468 cm21; H NMR 6200 MHz, CDCl3) d 2.39 6s, 3H),
3.48 6s, 3H), 3.506s, 3H), 5.34 6s, 2H), 6.90 6s, 2H,
±OH), 7.1±7.6 616H), 7.75 6s, 1H), 7.806d, J7.4 Hz,
1H), 7.88 6d, J8.0Hz, 1H); HRMS Calcd for C 41H32O7:
636.2148. Found: 636.2178; Anal. Calcd for C41H32O7: C,
77.34; H, 5.07. Found: C, 77.65; H, 4.94.
1
2946, 1503, 1423 cm21; H NMR 6200 MHz, CDCl3) d
3.58 6s, 6H), 3.73 6s, 6H), 7.15±7.60610H), 7.93 6s, 2H),
7.97 6d, J8.0Hz, 2H); HRMS Calcd for C 36H26O10F6S2:
796.0872. Found: 796.0901; Anal. Calcd for
C36H26O10F6S2: C, 54.27; H, 3.29. Found: C, 54.64; H, 3.48.
3.1.4. meso-Ternaphthalene 9. To a mixture of 8 65.40g,
8.5 mmol) and potassium carbonate 623.5 g, 170mmol) in
acetone 6500 ml) was dropwise added methyliodide 621 ml,
340mol) at room temperature. The mixture was re¯uxed for
2 h. After cooling, the reaction mixture was evaporated
3.1.6. Boric acid 12. To a solution of 11 63.00 g, 6.9 mmol)
in dry THF 630ml) was dropwise added n-butyllithium