C, 80.94; H, 9.26. Located: C, 80.67; H, 9.32. 4.two.6. 17,23-Epoxy-3-(phenylmethoxy)-19,24-dinorchola-1,three,5(ten)-triene (9)–To a resolution of 8 (56 mg, 0.14 mmol) in CHCl3 (2 mL) was added a drop of concentrated HCl. The mixture was allowed to stand stirred for 24 h at space temperature, and then passed by means of a short column of silica gel using hexanes thyl acetate as eluent. Concentration on the eluent gave 9 (50 mg, 89 ) as a colorless oil. +36 (c 1.0, CH2Cl2); 1H NMR (CDCl3, 300 MHz) 7.46?.28 (m, 5H), 7.22 (d, J = eight.four Hz, 1H), 6.87 (dd, J = two.7, eight.4 Hz, 1H), six.73 (d, J = 2.7 Hz, 1H), 5.04 (s, 2H), 3.87 (dt, J = four.5, 7.eight Hz, 1), three.62 (dt, J = 6.4, 7.eight Hz, 1H), 2.92?.82 (m, 2H), two.38?1.20 (m, 16H), 1.10 (d, J = 6.9 Hz, 3H), 0.74 (s, 3H); 13C NMR (CDCl3, 75 MHz) 155.eight, 137.six, 136.7, 132.8, 128.2, 127.three, 126.9, 125.8, 114.four, 111.eight, 95.5, 70.0, 66.0, 50.0, 48.2, 44.0, 39.three, 36.9, 35.1, 31.three, 31.0, 30.three, 28.1, 26.6, 23.6, 19.0, 15.eight. Anal. Calcd for C29H36O2: C, 83.61; H eight.71. Found: C, 83.35; H, 8.75. 4.2.7. 17,23-Epoxy-3-hydroxy-19,24-dinorchola-1,three,5(10)-triene (10)–To a answer of 9 (48.2628280-48-6 supplier 9 mg, 0.118 mmol) in methanol/CHCl3 (1:one hundred, 6 mL) was added 10 Pd on carbon (5.6 mg). The mixture was stirred beneath H2 (ca. 46 psi) within a Paar hydrogenation apparatus for three h. The catalyst was removed by filtration via filter-aid along with the filter bed was washed with copious CH2Cl2 along with the combined filtrates had been concentrated. The residue was purified by chromatography (SiO2, hexanes thyl acetate = 3:1) to afford 10 as a colorless solid (37.eight mg, 99 ). Mp 172?74 ; 1H NMR (CDCl3, 300 MHz) 7.15 (d, J = eight.four Hz, 1H), six.62 (dd, J = two.7, eight.four Hz, 1H), six.55 (d, J = 2.7 Hz, 1H), 3.87 (dt, J = 4.5, 7.eight Hz, 1H), 3.60 (dt, J = 6.3, eight.1 Hz, 1H), two.85?.75 (m, 2H), 2.35?.20 (m, 16H), 1.07 (d, J = 6.9 Hz, 3H), 0.70 (s, 3H); 13C NMR (CDCl3, 75 MHz) 153.three, 138.6, 133.2, 126.six, 115.4, 112.7, 96.0, 66.1, 50.0, 48.2, 43.9, 39.three, 36.8, 35.0, 31.two, 30.8, 30.0, 27.9, 26.4, 23.4, 18.8, 15.6. Anal. Calcd for C22H30O2?/4H2O: C, 79.83; H 9.29. Discovered: C, 80.12; H, 9.33. four.2.8. (20S) 3-Hydroxy-19,24-dinorchola-1,3,5(ten),16-tetraen-23-al (12)–To a option of 11 (one hundred mg, 0.Formula of H2N-PEG2-CH2COOtBu 296 mmol) in THF (4 mL) was added a resolution of ethyl magnesium bromide in THF (0.PMID:33593266 67 mL, 1.0 M, 0.67 mmol). The solution was stirred at space temperature for 15 min, and after that strong 1,1-(azodicarbonyl)dipiperidine (0.17 g, 0.67 mmol)NIH-PA Author Manuscript NIH-PA Author Manuscript NIH-PA Author ManuscriptBioorg Med Chem. Author manuscript; available in PMC 2015 January 01.McCullough et al.Pagewas added. The reaction mixture was stirred for 1 h, after which quenched with saturated aqueous NH4Cl and extracted quite a few occasions with ether. The combined ethereal extracts were dried (MgSO4), concentrated plus the residue was purified by column chromatography (SiO2, hexanes thyl acetate = 5:1) to afford 12 as a colorless strong (66 mg, 66 ). Mp +78 (c 0.80, acetone); 1H NMR (acetone-d6, 300 MHz) 9.66 (t, J = 168.five?71 , two.1 Hz, 1H), 7.06 (d, J = eight.four Hz, 1H), six.57 (dd, J = two.5, 8.4 Hz, 1H), six.51 (d, J = two.five Hz, 1H), 5.46 (br s, 1H), 2.90?.75 (m, 4H), two.62 (ddd, J = 1.eight, five.7, 16.2 Hz, 1H), 2.44?.30 (m, 2H), two.26?.10 (m, 2H), 1.98?.86 (m, 3H), 1.60?.34 (m, 5H), 1.16 (d, J = 7.2 Hz, 3H), 0.88 (s, 3H); 13C NMR (acetone-d6, 75 MHz) 203.2, 161.4, 156.8, 139.5, 133.three, 127.9, 124.6, 117.two, 114.eight, 59.2, 53.1, 50.2, 47.two, 40.5, 37.7, 33.6, 32.three, 30.7, 29.7, 29.four, 23.8, 19.3. Anal. Calcd for C22H28O2: C, 81.44; H, 8.70. Located: C, 81.21.