(S)-4,5-Dihydro-3H-dinaphtho[2,1-c:1′,2′-e]azepine

[97551-09-2] C22H17N (MW 295.38) InChI = 1S/C22H17N/c1-3-7-19-15(5-1)9-11-17-13-23-14-18-12-10-16-6-2-4-8-20(16)22(18)21(17)19/h1-12,23H,13-14H2 InChIKey = YZXDPXIVNVKRNR-UHFFFAOYSA-N (reagent used as a chiral auxiliary or a building block to form chiral reagents, ligands, and catalysts for asymmetric reactions) Alternative Names: 3H-dinaphth[2,1-c:1′,2′-e]azepine, 4,5-dihydro-, (11bS)-; 3H-dinaphth[2,1-c:1′,2′-e]azepine, 4,5-dihydro-, (S)-; (S)-3,5-dihydro-4H-dinaphth(2,1-c:1′,2′-e)azepine. Physical Data: mp 73–84 °C,1 white solidified foam,1 [α]D20 + 620° (c 0.78, CHCl3).1 Solubility: sol in THF, toluene, CHCl3, and most organic solvents; insol in water. Form Supplied in: available from Shanghai SynCores Technologies, Inc. and D-L Chiral Chemicals, LLC. Analysis of Reagent Purity: IR (KBr) 3382, 3049, 2957, 2862, 1595, 1508, 1463, 1446, 1398, 1364, 817, 752 cm−12; 1H NMR (500 MHz, CDCl3): δ 2.12 (br s, 1H), 3.53 (d, J = 11.7 Hz, 2H), 3.85 (d, J = 11.7 Hz, 2H); 7.23–7.31 (m, 2H), 7.43–7.50 (m, 4H), 7.58 (d, J = 8.3 Hz, 2H), 7.94–8.02 (m, 4H) ppm3; 13C NMR (125 MHz, CDCl3): δ 48.4, 125.2, 125.6, 126.8, 127.1, 128.1, 128.7, 131.2, 132.8, 134.6, 134.8 ppm3; Anal. calcd. for C22H17N: C 89.46, H 5.80, N 4.74; found: C 89.52, H 5.86, N 4.69.3 Preparative Methods: (S)-4,5-dihydro-3H-dinaphtho[2,1-c:1′,2′-e]azepine was first synthesized from (±)-2,2′-bis(bromomethyl)-1,1′-binaphthalene (eq 1).4 The reaction sequence involved alkylation of (R)-α-aminophenylacetamide and crystallization to obtain the pure diastereoisomer (R)-2-{(S)-3H- dinaphtho[2,1-c:1′,2′-e]azepin-4(5H)-yl}-2-phenylacetamide, followed by dehydration with POCl3 and CN bond cleavage with AgNO3 to give the optically pure final product. It has also been prepared from the same starting material through alkylation of 2,2,2-trifluoroacetamide, hydrolysis of the amide, and resolution of the racemate from the dibenzoyl-l-tartrate salt (eq 2).1 A simplified procedure involves the cyclization of (S)-2,2′-bis(bromomethyl)-1,1′-binaphthalene with allylamine with subsequent N-deallylation in the presence of 1,3-dimethylbarbituric acid (NDMBA) and Pd(OAc)2 (eq 3).2 (1) (2) (3) Purification: column chromatography on silica gel.2 Handling, Storage, and Precautions: keep container tightly closed in a dry and well-ventilated place. Handle with gloves. Avoid formation of dust and aerosols. Avoid breathing dust. Irritating to eyes, skin, and respiratory system. Related Reagents: (R)-4,5-dihydro-3H-dinaphtho[2,1-c:1′,2′-e]azepine; (S)-4,5-dihydro-3H-dinaphtho[2,1-c:1′,2′-e]azepine-2-carboxylic acid.