Diethyl Ether → (1s,2s)-2-(4-Cyanophenoxy)-1,2,-dihydro-naphthalen-1-ol

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Reaction Conditions

Reaction Steps

To a flame dried round-bottomed flask, [Rh(COD)Cl]2 (1.7 mg, 0.0035 mmol), (S)—(R)-PPF-PtBu2 (3.8 mg, 0.0069 mmol) and 1 (100 mg, 0.694 mmol) were added followed by addition of THF (2.5 mL) and 4-cyanophenol (413 mg, 3.47 mmol). The mixture was heated at 80° C. for 5 hours, then poured into diethyl ether and extracted 3 times with 10% aqueous sodium hydroxide solution. The aqueous extracts were combined and back-extracted three times with diethyl ether. The combined ether extracts were washed with brine and dried with anhydrous sodium sulfate. The solvents were removed in vacuo, yielding a solid which was purified by flash chromatography on silica gel (30% ethyl acetate in hexanes) giving a white crystalline solid 4 (160 mg, 88%). The ee was determined to be 97% by HPLC analysis on a CHIRALCEL OD column, λ=256 nm. Retention times in 3% isopropanol in hexanes were 35.3 min and 37.7 min (major). Fr=0.40 on silica (30% ethyl acetate in hexanes); mp 140-141° C. (Et2O); [α]25D=+182.3° (c=11.2, CHCl3) IR (KBr, cm−1) 3303 (b) 3050 (w) 2210 (m) 1598 (s) 1503 (s) 1238 (s) 1025 (m) 859 (m) 778 (m); 1H NMR (400 MHz, CDCl): δ 7.62-7.57 (3H, m), 7.33-7.27 (3H, m), 7.14-7.12 (1H, m), 6.56 (1H, dd, J=1.4, 9.7 Hz), 5.93 (1H, dd, J=1.4, 9.7 Hz), 5.20-5.13 (2H, m), 2.25 (1H, s). 13C NMR (400 MHz, CDCl3): δ 160.8, 135.0, 134.2, 131.5, 130.0, 128.5, 128.3, 126.7, 125.4, 124.4, 119.0, 116.2, 104.6, 79.2, 72.0. HRMS calcd for (M−H2O)+ (C17H11ON): 245.0841. Found: 245.0845.

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