4,5-Dihydro-4-phenyl-3H-dinaphtho[2,1-c:1′,2′-e]phosphepin

(R)[174390-35-3] C28H21P (MW 388.44) InChI = 1S/C28H21P/c1-2-10-24(11-3-1)29-18-22-16-14-20-8-4-6-12-25(20)27(22)28-23(19-29)17-15-21-9-5-7-13-26(21)28/h1-17H,18-19H2 InChIKey = NHIVGNHRQMUGNK-UHFFFAOYSA-N (S)[155898-25-2] C28H21P (MW 388.44) InChI = 1S/C28H21P/c1-2-10-24(11-3-1)29-18-22-16-14-20-8-4-6-12-25(20)27(22)28-23(19-29)17-15-21-9-5-7-13-26(21)28/h1-17H,18-19H2 InChIKey = NHIVGNHRQMUGNK-UHFFFAOYSA-N [155825-57-3] C28H21P (MW 388.44) InChI = 1S/C28H21P/c1-2-10-24(11-3-1)29-18-22-16-14-20-8-4-6-12-25(20)27(22)28-23(19-29)17-15-21-9-5-7-13-26(21)28/h1-17H,18-19H2 InChIKey = NHIVGNHRQMUGNK-UHFFFAOYSA-N Alternate Names: Ph-BINEPINE. Physical Data: mp 189–190 °C (CH2Cl2/hexane); [α]D25 −90.2 (c 0.8; CHCl3) for (S) enantiomer.1 (axially chiral monophosphanes-phosphepine derivatives, enantioselective catalysis, asymmetric organocatalysis) Solubility: sol THF, dichloromethane, chloroform, ethyl acetate, acetone; modestly sol diethyl ether, toluene; slightly sol hexane; insol water. Form Supplied in: white powder. Analysis of Reagent Purity: TLC analysis (E. Merck Kiesel-gel 60 PF254, hexane- ethyl acetate 2:1) Rf0.15 (Ph-BINEPINE oxide) and 0.9 (Ph-BINEPINE). 1H NMR (CDCl3) δ 2.71–3.06 (m, 4H), 6.90 (d, J = 8.4 Hz, Ar, 1H), 7.20–7.33 (m, Ar, 9H), 7.38–7.47 (m, Ar, 2H), 7.67 (dd, J = 0.9, 8.4 Hz, Ar, 1H), 7.71 (d, J = 8.4 Hz, Ar, 1H), 7.88 (d, J = 8.4 Hz, Ar, 1H), 7.94 (dd, J = 1.5, 8.4 Hz, Ar, 2H). 13C NMR (CDCl3) (aliphatic carbons only) δ 30.31 (d,1JC–P = 16.5 Hz), 32.20 (d, 1JC–P = 22.0 Hz); 31P-NMR (CDCl3) δ 6.97 (s). Preparative Methods: a solution of n-BuLi (12.8 mmol, 8 mL, 1.6 M in n-hexane) was concentrated under vacuum and the residual oil dissolved in diethyl ether (10 mL). After cooling to 0 °C, a solution of (S)-2,2′-dimethyl-1,1′-binaphthyl (5.3 mmol, 1.5 g) in diethyl ether (5 mL) was added via a dropping funnel over 20 min, giving a red solution. Afterward, TMEDA (13 mmol, 1.96 mL, distilled over CaH2) was added slowly and the resulting solution was kept for 24 h at room temperature and deep red crystals were formed. The supernatant solution was decanted via cannula and the crystals were washed three times with dry n–hexane (3 mL each time, removed by cannula). n-Hexane was then added (10 mL) and the suspension was cooled to −78 °C while a solution of phenyldichlorophosphine (5.3 mmol, 0.72 mL) in n-hexane (5 mL) was added dropwise. The white-yellowish suspension was warmed up slowly to room temperature and was stirred overnight. The reaction was quenched with water, and the organic layer was separated and dried over MgSO4. Ph-BINEPINE was purified by flash chromatography (hexane–dichloromethane 5:1) to provide the (S)-enantiomer as a white powder (0.7–0.9 g; 35–45%).2 Purification: the product may contain some phosphine oxide as the main impurity, as can be determined by TLC or by NMR (31P-NMR (CDCl3) δ 54–55). The oxide can be removed by flash chromatography. Handling, Storage, and Precautions: Ph-BINEPINE is substantially stable to air in the solid state. Slow oxidation to the oxide can occur upon standing in solution. Use of deareated solvents for solutions and tightly closed containers flushed with nitrogen or argon is recommended for prolonged storage.