2‐(4,5‐Dihydro‐4‐Phenyl‐2‐Oxazolyl)Phenol

( S )‐enantiomer image [135948‐05‐9] C 15 H 13 NO 2 (MW 239.27) InChI =  1S/C15H13NO2/c17‐14‐9‐5‐4‐8‐12(14)15‐16‐13(10‐18‐15)11‐6‐2‐1‐3‐7‐11/h1‐9,13,17H,10H2/t13‐/m1/s1 InChIKey =  IZKPOGDNFMTRFD‐CYBMUJFWSA‐N SMILES: C1[C@@H](N=C(O1)C2=CC=CC=C2O)C3=CC=CC=C3 Canonical SMILES: OC1=C(C=CC=C1)C1=N[C@H](CO1)C1=CC=CC=C1 ( R )‐enantiomer image [150699‐08‐4] C 15 H 13 NO 2 (MW 239.27) InChI =  1S/C15H13NO2/c17‐14‐9‐5‐4‐8‐12(14)15‐16‐13(10‐18‐15)11‐6‐2‐1‐3‐7‐11/h1‐9,13,17H,10H2/t13‐/m0/s1 InChIKey =  IZKPOGDNFMTRFD‐ZDUSSCGKSA‐N SMILES: C1[C@H](N=C(O1)C2=CC=CC=C2O)C3=CC=CC=C3 Canonical SMILES: OC1=CC=CC=C1C1=N[C@@H](CO1)C1=CC=CC=C1 racemate image [760952‐77‐0] C 15 H 13 NO 2 (MW 239.27) InChI =  1S/C15H13NO2/c17‐14‐9‐5‐4‐8‐12(14)15‐16‐13(10‐18‐15)11‐6‐2‐1‐3‐7‐11/h1‐9,13,17H,10H2 InChIKey =  IZKPOGDNFMTRFD‐UHFFFAOYSA‐N SMILES: C1C(N=C(O1)C2=CC=CC=C2O)C3=CC=CC=C3 Canonical SMILES: [H][C@@]1(COC(=N1)C1=C(O)C=CC=C1)C1=CC=CC=C1 (chiral ligand for the synthesis of N,O‐ligated metal complexes, 1–5 asymmetric allylic substitution reactions, 6 asymmetric functionalization of alkenes, 7–9 and enantioselective CH activation 10–15 ). Alternative Name(s) : 2‐(4‐phenyl‐4,5‐dihydrooxazol‐2‐yl)phenol, salicyloxazoline (Salox); phenol‐oxazoline. Physical Data : bp 185 °C/0.02 mbar,  = +40.4 ( c 2.27, toluene) for ( S )‐ 1 ; 1 mp 36–37 °C,  = +122.4° ( c 1.0, CHCl 3 ) for ( R )‐ 1 . 16 Solubility : soluble in most organic solvents such as dichloromethane, toluene, methanol, and ethyl acetate. Form Supplied in : white solid; commercially available. Analysis of Reagent Purity : 1 H NMR (400 MHz, CDCl 3 ) δ 12.14 (s, 1 H ), 7.72 (dd, J  = 7.6, 1.6 Hz, 1 H ), 7.43–7.28 (m, 6 H ), 7.04 (dd, J  = 8.4, 0.8 Hz, 1 H ), 6.90 (td, J  = 7.6, 1.2 Hz, 1 H ), 5.46 (dd, J  = 10.0, 8.4 Hz, 1 H ), 4.79 (dd, J  = 10.0, 8.4 Hz, 1 H ), 4.24 (t, J  = 8.0 Hz, 1 H ); 13 C NMR (101 MHz, CDCl 3 ) δ 166.3, 160.1, 141.6, 133.6, 128.9, 128.2, 127.9, 126.5, 118.7, 116.9, 110.5, 74.0, 68.8; HRMS (EI) calculated for [C 15 H 13 NO 2 ] + : 239.0946, found: 239.0946. 10 Preparative Methods : ZnCl 2 (79.5 mg, 0.583 mmol, 0.05 equiv) was added to a 100 mL round‐bottomed flask, placed under vacuum, and melted with a burner. Upon cooling and backfilling with N 2 , the oil resolidified and toluene (34 mL) was added to the flask. ( S )‐ α ‐phenylglycinol (16.9 mmol, 1.5 equiv) was added, followed by 2‐hydroxybenzonitrile (11.4 mmol, 1.0 equiv). The solution was heated to reflux at 130 °C under a N 2 atmosphere and maintained at this temperature for 24 h. Upon completion of the reaction, toluene was removed under reduced pressure. The crude residue was purified by flash column chromatography on silica gel (EtOAc:Hexanes = 6:94 v/v) to afford desired ( S )‐ 1 in 96% yield (eq 1). 10 An alternative method is also available. 17 To a Schlenk tube containing salicylic acid (10.0 mmol, 1 equiv), ( S )‐ α ‐phenylglycinol (10.0 mmol, 1 equiv), and triphenylphosphine (30.0 mmol, 3 equiv) was added acetonitrile (50 mL). To the resulting white suspension was added triethylamine (40.0 mmol, 4 equiv) with stirring, and a clear colorless solution was obtained. Carbon tetrachloride (100.0 mmol, 10 equiv) was added dropwise to the reaction mixture over 4 h, via syringe pump. During the addition of the CCl 4 , a precipitate formed and the reaction mixture changed color to dark‐red. The reaction was stirred for 48 h, resulting in a dark red suspension. The solution was then filtered, and the colorless residue was washed with diethyl ether (2 × 30 mL). The filtrate and washings were combined, the resulting precipitate was removed by filtration, and the process was repeated until no more solids precipitated. The filtrate was evaporated under reduced pressure to leave a sticky, dark red–brown residue, which was extracted with hexane (200 mL) overnight. The solvent was removed in vacuo. The product was purified via flash chromatography on silica gel using hexane/ethyl acetate as the mobile phase. image Handling, Storage, and Precautions : the title compound is a white solid that is stable at room temperature. No biological activity/toxicity has been reported. For safety reasons, standard procedures for handling potentially toxic solids should be employed.