D. Liu et al.
432
rt. The mixture was extracted with dichloromethane (2 × 20 mL), and the
combined organic layers were dried over sodium sulfate, filtered, and con-
centrated in vacuo. Flash chromatography (silica gel, 40:1 hexanes/ethyl ac-
etate → 20:1 hexanes/ethyl acetate) afforded the title product (76 mg, 45%
26.5◦C
yield over two steps). mp >292◦C (dec.); α
α
[ ]D
= +35 (S, c 0.75, CHCl3);
[ ]D
27.7◦C
1
= −33 (R, c 1.3, CHCl3). H NMR (500 MHz, CDCl3): δ = 7.22 (d, J
= 1.8 Hz, 2H), 7.19 (d, J = 1.8 Hz, 2H), 6.83 (s, 2H), 4.40 (s, 2H), 2.72−2.85
(m, 6H), 2.66 (septet, J = 6.8 Hz, 2H), 2.30−2.47 (m, 4H), 2.11 (m, 6H), 1.97
(mc, 12H), 1.70−1.85 (m, 20H), 1.15 (d, J = 6.9 Hz, 6H), 1.11 (d, J = 6.9 Hz,
6H), 1.06 (d, J = 6.9 Hz, 6H), 1.00 (d, J = 6.9 Hz, 6H). 13C NMR (125 MHz,
CDCl3): δ = 150.8, 148.5, 147.3, 147.1, 135.8, 131.1, 130.9, 129.0, 124.1,
120.5, 119.3, 119.2, 43.2, 36.9, 36.4, 30.8, 30.7, 29.2, 29.1, 27.0, 24.3, 24.1,
23.9, 23.2, 23.1. MS (ESI) m/z: calcd for C64H82O2Na [M+Na]+ 905.6, found:
905.5. HRMS (ESI) m/z: calcd for C64H82O2Na [M+Na]+ 905.6207, found
905.6228
(S or R)-3,3ꢁ-Bis[4-(1-adamantyl)-2,6-diisopropylphenyl]-5,5ꢁ,6,6ꢁ,7,7ꢁ,8,8ꢁ-
octahydro-1,1ꢁ-binaphthyl phosphate (11). Phosphorous oxychloride (0.14 mL,
4.2 eq) was slowly added to a solution of (S)-3,3ꢁ-bis[4-(1-adamantyl)-2,6-
diisopropylphenylꢁ-5,5ꢁ,6,6ꢁ,7,7ꢁ,8,8ꢁ-octahydro-2,2ꢁ-dihydroxy-1,1ꢁ-binaphthyl
(0.32 g, 0.37 mmol, 1.0 eq) in pyridine (3.6 mL) at rt. The reaction mixture
was then heated to 90◦C for 17 h, then cooled to rt. The reaction was then
treated with water (3.6 mL) and heated to 90◦C for 6 h. After cooling to rt,
the solvent was removed in vacuo, and the residue was partitioned between
dichloromethane (30 mL) and 6 N HCl (10 mL). The aqueous layer was ex-
tracted with dichloromethane (30 mL), and the combined organic layers were
dried over sodium sulfate, filtered, and concentrated in vacuo. The residue was
purified by flash chromatography (silica gel, 100% dichloromethane → 50:1
dichloromethane/methanol → 20:1 dichloromethane/methanol). The product
was partitioned between dichloromethane (50 mL) and 4 N HCl (10 mL), and
the organic layer was dried over sodium sulfate, filtered, and concentrated
to provide 10 (289 mg, 83% yield) as a pale yellow solid. Analytically pure
compound could be obtained by further flash chromatography on silica gel
using hexanes/ethyl acetate (1:1) and acidifying with 4 N HCl. mp >270◦C
27.2◦C
1
(dec.); α
= +89 (S, c 0.49, CHCl3); −85 (R, c 0.40, CHCl3). H NMR
[ ]D
(500 MHz, CDCl3): δ = 7.04 (d, J = 1.6 Hz, 2H), 7.02 (d, J = 1.6 Hz, 2H),
6.94 (s, 2H), 2.74−2.89 (m, 6H), 2.59 (septet, J = 6.8 Hz, 2H), 2.45−2.57
(m, 2H), 2.27−2.38 (m, 2H), 2.06 (m, 6H), 1.68−1.95 (m, 32H), 1.07 (d, J =
6.7 Hz, 6H), 0.98 (m, 6H), 0.89 (d, J = 6.8 Hz, 6H), 0.79 (m, 6H). 13C NMR
(125 MHz, CDCl3): δ = 150.0, 147.2, 146.6, 144.2 (J = 9.0 Hz), 136.5, 133.8,
132.6, 131.5, 129.6, 126.9, 119.2, 118.3, 43.2, 37.0, 36.3, 30.8, 30.7, 29.3, 29.1,
27.9, 26.7, 25.1, 23.5, 23.0, 22.9. MS (ESI) m/z: calcd for C64H80O4P [M-H]−