ࡱ> AC@yM Gbjbj== "nWWq3\lPPPPPPPd8.<jdR&<<<   acccccc$0 PJP     +PP<<+++ P<P<a+ a++PP< ?d*\0++ddPPPPProgress Toward the Total Synthesis of Kalihinane Diterpenoids Ryan D. White and John L. Wood* Sterling Chemistry Laboratory, Department of Chemistry, Yale University, New Haven, Connecticut 06520-8107 ________________________________________________________________________ Material and Methods Unless otherwise stated, reactions were performed under a nitrogen atmosphere using freshly distilled solvents. Diethyl ether (Et2O) and tetrahydrofuran (THF) were distilled from sodium/benzophenone. Methylene chloride (CH2Cl2), and benzene were distilled from calcium hydride. Methanol (MeOH) was distilled from magnesium. All other commercially obtained reagents were used as received. All reactions were magnetically stirred and monitored by thin-layer chromatography (TLC) using E. Merck silica gel 60 F254 pre-coated plates (0.25-mm). Column or flash chromatography was performed with the indicated solvents using silica gel (particle size 0.032-0.063 nm) purchased from Bodman. 1H and 13C NMR spectra were recorded on Bruker Avance DPX-500 or Bruker Advance DPX-400 spectrometers. Chemical shifts are reported relative to internal chloroform (1H, ( 7.26 ppm, 13C ( 77.0 ppm), benzene (1H, ( 7.30 ppm), dimethyl sulfoxide (13C, ( 40.5 ppm), or methanol (13C, ( 49.9 ppm). Melting points were obtained on a Gallenkamp variable temperature melting point apparatus and are uncorrected. Infrared spectra were recorded on a Midac M-1200 FTIR. High resolution mass spectra were acquired at The University of Illinois Mass Spectrometry Center. _______________________________________________________________________ ________________________________________________________________________ Preparation of epoxide 4.  EMBED ChemDraw.Document.4.5  To a 0.09 M solution of dimethyl dioxirane in acetone (145 mL) at 78C, was added olefin 3 (1.52 g, 7.29 mmol) in acetone (10mL). After 2h, the solution was warmed to 25C and the solvent was removed in vacuo. The resulting oil was purified by silica gel column chromatography (hexanes:EtOAc, 15:1 then hexanes:EtOAc, 8:1) to give epoxide 4 (1.55 g, 95% yield) as a colorless oil. 1H NMR (400 MHz, CDCl3) 2.67 (s, 1H), 2.43 (t, J=7.1 Hz, 3H), 2.17 (m, 1H), 1.96-1.70 (comp. m, 6H), 1.43 (m, 1H), 1.36-1.22 (comp. m, 4H), 1.03 (d, J= 7.0 Hz, 3H), 0.96 (d, J=7.0 Hz, 3H); 13C NMR (125 MHz, CDCl3)  213.3, 64.3, 58.4, 44.7, 42.3, 38.7, 38.4, 28.4, 26.2, 23.9, 23.3, 21.7, 19.5, 19.1; IR (thin film/NaCl) 2958 (s), 2872 (s), 1708 (s), 1463 (m), 1420 (m), 1379 (m), 1223 (w), 963 (w),880 (w), 794 (m) cm-1; HRMS (EI) m/z found: 223.1698 [calc d for C14H23O2 (M+H): 223.1698]. ______________________________________________________________________ Preparation of trans-decalin 4A.  EMBED ChemDraw.Document.4.5  To a solution of epoxide 4 (4.69 g, 20.9 mmol) in MeOH (50 mL) at 35C was added NaOMe (60 mg, 1.11 mmol). After 36 h the solution was cooled to 25C, the volume was reduced in vacuo (ca.10 mL), diluted with CH2Cl2 (100 mL), and washed with H2O (2 x 25 mL) and brine (25 mL). After drying (Na2SO4), concentration in vacuo gave a 3:1 mixture of 4A:4 which could be used without further purification or purified by silica gel chromatography (hexanes:EtOAc, 15:1 then hexanes:EtOAc, 8:1) to afford pure 4A (3.42 g, 70% yield) as a colorless oil. 1H NMR (500 MHz, CDCl3) 2.98 (s, 1H), 2.40-2.24 (comp. m, 3H), 2.10-1.98 (m, 2H), 1.93 (br t, J= 11.9 Hz, 1H), 1.84-1.71 (m, 2H), 1.70-1.46 (m, 3H), 1.31 (s, 3H), 1.29-1.15 (m, 1H), 1.02 (d, J=7.0 Hz, 3H), 0.85 (d, J=7.0 Hz, 3H); 13C NMR (125 MHz, CDCl3)  211.7, 61.2, 58.8, 50.4, 44.7, 43.9, 40.5, 29.7, 27.1, 25.1, 23.9, 21.9, 19.3, 15.9; IR (thin film/NaCl) 2958 (s), 2874 (s), 1715 (s), 1452 (m), 1424 (m), 1370 (m), 1301 (w), 1019 (w), 888 (m), 791 (m) cm-1; HRMS (EI) m/z found: 223.1698 [calc d for C14H23O2 (M+H): 223.1698]. ________________________________________________________________________ Preparation of olefin 5.  EMBED ChemDraw.Document.4.5  To a solution of DMSO (16.2 mL) and THF (10 mL) was added 60% NaH (1.8 g, 42 mmol). The resulting mixture was heated at 60C for 4 h then cooled to 25C before adding a solution of methyltriphenylphosphonium iodide (16.92 g, 42.0 mmol) in THF (40 mL) over 5 minutes. To the yellow mixture was added a crude solution of decalins 4A:4, 3:1 (4.64 g, 20.7 mmol) in THF (100 mL). After heating at 50C for 3 h, then 25C for an additional 3 h, the reaction was quenched with H2O (50 mL) and diluted with hexanes (100 mL). The aqueous layer was separated and extracted with hexanes (3 x 25 mL) and the combined organic fractions were washed with H2O (3 x 50 mL), dried (NaSO4), and concentrated. The resulting residue was purified by silica gel column chromatography (Pentane:Et2O, 9:1) to give 3.50 g ( 76% yield from 4) of olefin 5 as a colorless oil. 1H NMR (500 MHz, CDCl3)  4.64 (d, 1.5 Hz, 1H), 4.48 (d, 1.5 Hz, 1H), 2.95 (s, 1H), 2.34 (dt, J=12.5, 6.7 Hz, 1H), 2.26 (m, 1H), 2.09 (m, 1H), 1.97 (dt, J=13.0, 4.3 Hz), 1.82 (ddd, J=12.7, 6.8, 3.5 Hz, 1H), 1.65 (ddd, J=13.5, 12.6, 5.7 Hz, 1H), 1.60 (ddt, J=12.8, 6.0, 2.0 Hz, 1H), 1.51 (br t, J=11.5 Hz, 1H), 1.44 (tt, J=12.0, 3.5Hz, 1H), 1.36-1.24 (comp. m, 5H), 1.14 (dq, J=13.0, 4.1 Hz, 1H), 0.96 (d, J=7.0, 3H), 0.91 (d, J=7.0 Hz, 3H); 13C NMR (125 MHz, CDCl3)  152.6, 104.6, 61.5, 58.6, 46.2, 45.2, 44.0, 36.4, 30.6, 27.2, 26.7, 24.1, 22.9, 22.0, 15.9; IR (thin film/NaCl) 2957 (s), 2933 (s), 2875 (m), 2842 (m), 1649 (w), 1449 (w), 1378 (w), 887 (m), 807 (w) cm-1; HRMS (EI) m/z found: 221.1905 [calcd for C15H25O (M+H): 221.1905]. ________________________________________________________________________ Preparation of azide 6.  EMBED ChemDraw.Document.4.5  To a solution of olefin 5 (3.45 g, 15.7 mmol) in 8:1 MeOH/H2O (150 mL), was added NaN3 (6.11 g, 94.0 mmol) and NH4Cl (2.51 g, 47.0 mmol). The mixture was heated to 80C. After 36 h, the mixture was cooled to 25C and the solvent volume reduced to ca. 50 mL and diluted with hexanes (50 mL) and EtOAc (50 mL). The aqueous layer was separated and extracted with EtOAc (2 x 25 mL) and the combined organic fractions were washed with brine (2 x 25 mL), dried (NaSO4), and concentrated to give spectroscopically pure azide 6 (4.12 g, 99% yield) as a colorless oil. 1H NMR (500 MHz, CDCl3)  4.68 (d, 1.5 Hz, 1H), 4.56 (d, 1.5 Hz, 1H), 3.50 (s, 1H), 2.36 (dt, J=13.0, 3.5 Hz, 1H), 2.02-1.93 (m, 2H), 1.88 (br t, J=11.2 Hz, 1H), 1.82 (ddd, J=18.6, 7.0, 3.5 Hz, 1H), 1.73-1.63 (comp. m, 3H), 1.62-1.47 (comp. m, 3H), 1.42 (br s, 1H), 1.36 (s, 3H), 1.13 (dq, J=12.4, 3.5 Hz, 1H), 0.99 (d, J=7.0, 3H), 0.76 (d, J=7.0 Hz, 3H); 13C NMR (125 MHz, CDCl3)  152.7, 105.4, 72.8, 68.5, 44.4, 43.6, 38.8, 36.6, 33.3, 29.2, 26.5, 26.3, 24.3, 21.8, 15.7; IR (thin film/NaCl) 3439 (br w), 2959 (m), 2935 (m), 2868 (m), 2104 (vs), 1644 (w), 1465 (w)1280 (m), 890 (m) cm-1; HRMS (EI) m/z found: 264.2075 [calcd for C15H26N3O (M+H): 264.2076]. ________________________________________________________________________ Preparation of aziridine 7.  EMBED ChemDraw.Document.4.5  To a solution of azide 6 (1.26 g, 4.80 mmol) in dry MeCN (250 mL) with 4 sieves (ca. 3 g) at 25C, was added N-tosyliminophenyliodinane (3.59 g, 9.61 mmol). After 5 minutes, Cu(Otf)2 (87 mg, 0.24 mmol) was added and the mixture was vigorously stirred for 8 h. EtOAc (50 mL) was added and the mixture was filtered through a short silica gel plug. After solvent removal in vacuo, the resulting residue, a 9:1 mixture of aziridine diastereomers, was purified by silica gel column chromatography (hexanes:EtOAc, 11:1) to afford aziridine 7 (1.65 mg, 82% yield) as a white solid. m.p. >143C (dec). 1H NMR (500 MHz, CDCl3)  7.80 (d, 8.5 Hz, 2H), 7.30 (d, 8.5 Hz, 2H), 3.49 (br s, 1H), 2.50 (s, 1H), 2.43 (s, 3H), 2.37 (d, J=1.7 Hz, 1H), 2.27 (dt, J=13.3, 3.5 Hz, 1H), 2.11 (m, 1H), 2.02-1.89 (comp. m, 2H), 1.78 (dt, J=11.2, 2.5 Hz, 1H), 1.61-1.46 (comp. m, 5H), 1.40-1.34 (comp. m, 1H), 1.34 (s, 3H), 1.19 (dq, J=13.1, 3.5 Hz, 1H), 1.00 (d, J=13.1 Hz, 3H), 0.99-0.88 (comp. m, 1H), 0.79 (d, J=13.1 Hz, 3H); 13C NMR (125 MHz, CDCl3)  144.0, 138.7, 129.8, 127.6, 72.5, 68.2, 55.7, 42.9, 42.2, 38.1, 36.9, 32.8, 31.6, 29.3, 26.3, 24.1, 22.0, 21.7, 20.5, 15.7; IR (thin film/NaCl) 3507 (br w), 2958 (m), 2870 (w), 2099 (s), 1313 (m), 1288 (m), 1156 (m)1094 (w), 718 (m) cm-1; HRMS (EI) m/z found: 433.2274 [calcd for C22H33N4O3S (M+H): 433.2273]. ________________________________________________________________________ Preparation of amine 8.  EMBED ChemDraw.Document.4.5  To a solution of aziridine 7 (617 mg, 1.43 mmol) in 3:1 MeOH/THF (30 mL) at 0C was added NiCl26H2O (542 mg, 2.28 mmol) followed by NaBH4 (248 mg, 6.57 mmol) over 10 minutes. After 30 minutes the black mixture was allowed to warm to 25C, diluted with EtOAc (40 mL), and filtered through celite. The solution was further diluted with EtOAc (50 mL) and washed with brine (2 x 25 mL) and 0.01M EDTA solution (1 x 25 mL, pH 7.5, K-phosphate buffer). After solvent removal in vacuo, the resulting oil was purified by silica gel column chromatography (EtOAc, 100% then EtOAc: MeOH, 12:1) to give 569 mg (98% yield) of amine 8. 1H NMR (500 MHz, CDCl3)  7.80 (d, 8.5 Hz, 2H), 7.30 (d, 8.5 Hz, 2H), 2.76 (br s, 1H), 2.52 (s, 1H), 2.43 (s, 1H), 2.42(s, 3H), 2.28 (dt, J=13.2, 3.5 Hz, 1H), 2.10 (br t, J=13.0 Hz, 1H), 1.92 (comp. m, 3H), 1.73 (br t, J=11.3 Hz, 1H), 1.62 (br t, J=11.6 Hz, 1H), 1.52-1.14 (comp. m, 9H), 0.98 (m, 1H), 0.96 (d, J=7.8 Hz, 3H), 0.77 (d, J=7.8 Hz, 3H); 13C NMR (125 MHz, CDCl3)  143.9, 138.8, 129.8, 127.6, 56.3, 55.7, 42.6, 41.8, 37.4, 37.2, 32.1, 31.9, 29.2, 25.8, 24.3, 22.0, 21.9, 20.8,15.8; IR (thin film/NaCl) 3522 (br w), 2955 (m), 2870 (m), 1598 (w), 1465 (w), 1384 (w), 1369 (w),1156 (s), 1094 (m),1005 (m),716 (s) cm-1; HRMS (EI) m/z found: 407.2368 [calcd for C22H35N2O3S (M+H): 407.2368]. _______________________________________________________________________ Preparation of amine 9.  EMBED ChemDraw.Document.4.5  To a solution of amine 8 (703 mg, 1.73 mmol) in THF (30 mL) at 0(C was added 1M Li(Et)3BH in THF (8.7 mL, 8.7 mmol). The reaction mixture was stirred at 0C for 1 h, then warmed to 40C. After 10 h, the mixture was cooled to 0C and diluted with EtOAc (50 mL) and H2O (15 mL). The organic layer was separated, washed with brine (2 x 20 mL), and dried (Na2SO4). After solvent removal in vacuo, the residue was purified by silica gel column chromatography (EtOAc then EtOAc:MeOH, 10:1) to afford amine 9 (664 mg, 94% yield) as a colorless oil. 1H NMR (500 MHz, CDCl3)  7.67 (d, 17.0 Hz, 2H), 7.18 (d, 17.0 Hz, 2H), 4.41 (s, 1H), 2.62 (s, 1H), 2.33 (s, 3H), 1.82-1.71 (m, 2H), 1.63 (dt, J=20.0, 6.0 Hz, 1H), 1.52-1.04 (comp. m, 16H), 1.02 (s, 3H), 0.96 (m, 1H), 0.79 (d, J=13.0 Hz, 3H), 0.63 (d, J=13.0 Hz, 3H); 13C NMR (125 MHz, CDCl3)  143.2, 141.3, 129.8, 128.7, 127.4, 72.6, 61.1, 55.7, 42.4, 42.2, 39.8, 38.3, 32.7, 29.2, 25.7, 22.0, 21.9, 21.5, 20.4, 19.9, 15.7; IR (thin film/NaCl) 3503 (br w), 3276 (m), 2955 (s), 2933 (s), 2870 (s), 1598 (w), 1456 (m), 1384 (m), 1322 (m), 1150 (s), 1093 (s), 732 (s) cm-1; HRMS (EI) m/z found: 409.2526 [calcd for C22H37N2O3S (M+H): 409.2525]. ________________________________________________________________________ Preparation of bis-isonitrile 11.  EMBED ChemDraw.Document.4.5  To condensed ammonia (40 mL) at 78C was added sodium (300 mg, 13 mmol) followed by 9 (530 mg, 1.30 mmol) in THF (8 mL). After 3 h, the blue mixture was warmed to reflux for an additional 2 h. The ammonia was allowed to evaporate until the reaction mixture volume was ca. 10 mL, then the reaction was quenched with saturated ammonium chloride (5 mL) and diluted with EtOAc (30 mL). The organic layer was washed with 0.1 M NaOH (2 x 10 mL), brine (1 x 10 mL) and dried (Na2SO4). After concentration, the resulting oil was dissolved in THF (10 mL) to which a 0.5 M solution of N-formyl imidazole in CH2Cl2 (4 ml) was added. After 8 h at room temperature, the solvent was removed in vacuo and the residue taken up in Et2O (3 mL) and filtered through celite. After concentration, the resulting oil was diluted with CH2Cl2 (15 mL). To this solution was added pyridine (80 L, 0.99 mmol) followed by p-toluenesulphonyl chloride (189 mg, 0.990 mmol). After 12 h at room temperature, the solvent was removed in vacuo and the residue purified by silica gel column chromatography (hexanes:EtOAc, 9:1) to afford 270 mg (76% yield from 9) of isonitrile 11 as a white solid. 1H NMR (400 MHz, CDCl3)  3.49 (s, 1H), 1.92 (dt, J= 12.9, 3.4 Hz, 1H), 1.79-1.29 (comp. m, 10H), 1.29 (s, 3H), 1.22 (br s, 1H), 1.18 (t, J=2.3 Hz, 3H), 0.98 (dq, J=12.7, 3.4 Hz, 1H), 0.80 (d, J=7.0 Hz, 3H), 0.59 (d, J=7.0 Hz, 3H); 13C NMR (100 MHz, CDCl3)  158.8 (t, J=5.0 Hz), 153.2 (t, J=5.0 Hz), 70.6, 61.2, (t, J=5.0 Hz), 60.6, (t, J=5.0 Hz), 43.1, 42.6, 40.7, 36.4, 33.0, 29.1, 25.8, 21.7, 21.4, 21.2, 19.5, 15.4; IR (thin film/NaCl) 3419 (br m), 2955 (s), 2873 (m), 2273 (w), 2133 (vs), 1467 (w), 1385 (m), 1179 (w), 1125 (w), 1002 (m), 733 (w) cm-1; HRMS (EI) m/z found: 275.2123 [calcd for C17H27N2O (M+H): 275.2124]. White et al. 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