; H, eight.54. four.two.9. 17,23-Epoxy-3-hydroxy-19-norchola-1,three,five(10)-triene (13)–To a answer of 12 (45.9 mg, 0.142 mmol) in THF (7 mL) at 0 was added a resolution of methyl magnesium bromide in ether (0.10 mL, 3.0 M, 0.30 mmol). The reaction mixture was stirred for three h, and after that quenched with saturated aqueous NH4Cl (15 mL). The mixture was extracted quite a few occasions with CH2Cl2 along with the combined extracts have been dried (MgSO4) and concentrated. The residue was purified by chromatography (SiO2, hexanes thyl acetate = 5:1) to afford 13 as a colorless solid (44 mg, 92 ). Analysis in the product by 1H NMR spectroscopy indicated this to be a 1:1 mixture of diastereomers. Mp 248?51 , 1H NMR (CDCl3, 300 MHz) 7.15 (d, J = eight.four Hz, 1H), six.62 (dd, J = 2.7, eight.four Hz, 1H), 6.56 (d, J = 2.7 Hz, 1H), 4.18?.07 (m, 1H), three.85?.74 (m, 1H), 2.85?.75 (m, 2H), 2.35?.20 (m, 15H), 1.23 1.20 (2 ?d, J = 5.7 Hz, 3H total), 1.07 1.05 (two ?d, J = 6.9 Hz, 3H), 0.72 0.66 (2 ?s, 3H total); 13C NMR (CDCl3, 75 MHz) 153.three, 138.six, 133.2, 126.six, 115.4, 112.7, 97.1 [95.8], 73.six [71.3], 49.85 [49.80], 48.eight, 47.1, 45.4, 43.9 [43.8], 43.five, 39.3 [39.2], 36.two, 34.5, 32.3, 31.2 [30.9], 30.6 [30.1], 27.eight, 26.five [26.4], 23.5 [23.4], 21.six, 19.2 [18.9], 16.three [14.9]. Anal. Calcd for C23H32O2?/2H 2O: C, 79.04; H, 9.52. Identified: C, 79.34; H, 9.57. 4.2.ten. cis- and trans-4-(4-Hydroxycyclohexyl)phenol (14)–To a remedy of 4(4-hydroxyphenyl)cyclohexanone (50 mg, 0.26 mmol) in methanol (1 mL) was added NaBH4 (15 mg, 4.0 mmol). The reaction mixture was stirred for 30 min, and then diluted with water. The mixture was extracted many instances with ethyl acetate along with the combined extracts had been concentrated and purified by column chromatography (SiO2, hexanes thyl acetate = two:1) to afford cis-14 (5.0 mg, ten ) followed by trans-15 (43 mg, 86 ) both as colorless solids. Cis-14: 1H NMR (CD3OD, 400 MHz) 7.04?.69 (AABB, JAB = eight.eight Hz, 4H), four.Buy347186-01-0 02 (narrow t, J = two.8 Hz, 1H), two.50?.40 (m, 1H), 1.91?.79 (m, 4H), 1.69?.52 (m, 4H); 13C NMR (CD3OD, 75 MHz) 156.five, 140.1, 128.eight, 116.1, 66.five, 44.5, 34.0, 29.four. Trans-15: 1H NMR (CD3OD, 400 MHz) 7.01?.68 (AABB, JAB = eight.4 Hz, 4H), three.58 (tt, J = four.four, 10.six Hz, 1H), 2.39 (tt, J = 3.five, 11.eight Hz, 1H), 2.06?.99 (m, 2H), 1.87?.79 (m, 2H), 1.56?.33 (m, 4H). four.2.11. 4-(4-Hydroxyphenyl)-cyclohexanone oxime (16)–To a resolution of 4-(4hydroxyphenyl)cyclohexanone (50 mg, 0.26 mmol), hydroxylamine hydrochloride (36.6 mg, 0.526 mmol) in ethanol (five mL) was added Amberlyst (56 mg). Soon after stirring for 2 h, the mixture was filtered, and also the filtrate concentrated. The residue was partitioned betweenNIH-PA Author Manuscript NIH-PA Author Manuscript NIH-PA Author ManuscriptBioorg Med Chem.BuyPd 122 Author manuscript; out there in PMC 2015 January 01.PMID:33706827 McCullough et al.Pagewater and ethyl acetate, and also the organic layer was concentrated and dried to give (?-16 (44 mg, 82 ) as a colorless strong. Mp 172?75 . 1H NMR (CD3OD, 400 MHz) 7.03?.69 (AABB, JAB = 8.eight Hz, 4H), 4.02 (narrow t, J = two.eight Hz, 1H), two.0?.40 (m, 1H), 1.91?.79 (m, 4H), 1.69?.52 (m, 4H); 13C NMR (CD3OD, 75 MHz) 161.0, 156.8, 138.four, 128.7, 116.3, 44.3, 36.0, 34.7, 33.0, 25.2. HRMS (ESI): m/z calcd for C12H15NO2+Na+ [M+Na]+ 228.0995, located 228.0997. four.2.12. cis-1-Hydroxymethyl-4-(4-hydroxyphenyl)-cycloheptane (18)–To a resolution of (?-17 (75 mg, 0.35 mmol) in methanol (15 mL) within a heavy walled reaction vessel, was added a catalytic amount of 20 Pd/C. The mixture was stirred below H2 stress (45 psi) for 75 min and after that the reaction mixture w.