, 257 1.1.1 -Synthesis and transition metal-catalyzed cycloisomerization of cyclopropene-ene 71 257 1.1.2 -Determination of the relative configuration of 3-oxabicyclo 260 1.1.3 -Gold-catalyzed cycloisomerization of cyclopropene-ene 34 262 1.1.4 -Synthesis of cyclopropene-ene 81, p.264
, 266 1.2.1 -Synthesis and gold-catalyzed cycloisomerization of allylcyclopropenyl-carbinyl ethers derived from cyclopropenylcarbinol 70, p.270
, Synthesis of allylcyclopropenylcarbinyl ethers 99 275 1.2.2.2 -Synthesis and determination of the relative configuration of cyclopropenylcarbinols 101 and 102, ., p.284
, Catalaytic Isomerization of 1,5-Enynes to Bicyclo[3.1.0]hexenes, Journal of the American Chemical Society, vol.126, issue.35, pp.10858-10859, 2004.
DOI : 10.1021/ja046248w
, [?] D ?100.7 (c 0 CHCl 3 ), 2H, H 12 ), 4.48 (d, AB syst, J = 11.8 Hz, 1H, H 9 ), pp.3191-3194, 1000.
, 30 (s, 3H38 (m, 1H, H 7 ), 1.74 (s, 3H, H 15 or H 17, (m, 1H, H 4 ), 1.08 (d, J = 6.9 Hz, pp.3-4631
, 03 (s, 3H, H 14 or H 15 ), 0.88 (s, 3H, H 15 or H 14 ); 13 C NMR (100 MHz, CDCl 3 ) ? 143.3 (s, C 9 ), 138.2 (s, C 5 or C 12 ), 137.8 (s, C 12 or C 5 ), pp.39-55
, 81 (br s, 1H
, 04 (apparent dq, J = 10.2 Hz and J = 1, J = 17.2 Hz and J = 1.5 Hz, pp.4-53, 2006.
, 39 (s, 3H, H 15 ), 1.00 (s, 3H, H 16 or H 17, pp.0-96
, 16 (ddd, J = 7.3 Hz, J = 5.8 Hz and J = 1, pp.71-72, 2004.
, 65 (dd, J = 9.9 Hz and J = 6.2 Hz, 1H, pp.70-73
, 5 (s, 2C, C 24 ), 131.5 (d, C 19 or C 20 ), 131.2 (s, C 3 ), pp.5550-63
, 85 (s, 1H, H 6 ), 3.64 (d, AB syst, J = 13.8 Hz, 1H, H 1 ), 2.80 (d, AB syst, J = 13, pp.31-38, 1093.
, 27 (dd, J = 10.5 Hz and J = 5.6 Hz35 (s, 3H, H 20 ), 1.72 (s, 6H, H 13 +H 15 ), 1.42 (ddd, apparent td, J = 8.5 Hz and J = 4.8 Hz, 1H, H 4 ), 0.99 (m, 1H ); 13 C NMR (100 MHz, CDCl 3 ) ? 142.5 (s, C 16 ), 138.12 (s, C 9 or C 19 ), 138.07 (s, C 19 or C 9 ), 3.26 (dd, J = 13.2 Hz and J = 3.8 Hz, 1H, H 1' ), pp.7151-72, 2003.
, HRMS calcd for C 24 H 29 NO 3 SNa (M+Na + ): 434.17604, pp.92-91
, 81 (ddt, J = 17.2 Hz, J = 10.1 Hz and J = 7.2 Hz, 1H, H 9 ), p.88, 2003.
, 4.46 (d, AB syst, J = 11.2 Hz, 1H, H 6' ), 3.80 (s, 3H, p.6659
, 28 (s, 3H, H 15 ), 0.22 (s, 3H, H 15' ), 0.19 (m, 1H, H 1 ); 13 C NMR (100 MHz, CDCl 3 ) ? 139.8 (s, C 16 (s, C 4 or C 13, pp.66-128
, To a solution of alcohol 70 (101 mg, 0.465 mmol) Et 3 N (0.16 mL, 1.2 mmol, 2.5 equiv) and DMAP (11.4 mg, 0.093 mmol, 0.2 equiv) in CH 2 Cl 2 (0.8 mL) at 0 °C, was added allyldimethylchlorosilane (0.084 mL, 0.56 mmol, 1.2 equiv) After 0.5 h at rt, pentane was added and the resulting suspension was filtered through a pad of Celite (pentane) The filtrate was concentrated under reduced pressure and the residue was purified by flash chromatography (petroleum ether/EtOAc: 97/3) to afford 138 mg (94%) of silyl ether 174 as a colorless oil, pp.696-697, 1029.
, 03 (m, 1H, H 10' ), 4.74 (t, J = 1.5 Hz, 2H, H 8 ); 13 C NMR (100 MHz, CDCl 3 ) ? 189, pp.50-121
, Fe/Cr- and Co/Cr-Mediated Catalytic Asymmetric 2-Haloallylations of Aldehydes, Journal of the American Chemical Society, vol.126, issue.39, pp.12248-12249, 2004.
DOI : 10.1021/ja045557j
, 1H, H 3 ); 13 C NMR (100 MHz, CDCl 3 ) ? 160.3 (s, C 10 ), 159.5 (s, C 12 ), 133.2 (s, C 5 or C 14 ), 133.0 (s, C 14 or C 5 ), pp.48-74
, 8 Hz, 1H, H 3' ), 0.50 (apparent dt
, 06 (m, 1H, H 1' ), 1.85 (s, 3H, H 13 or H 15 ), 1.72 (s, 3H, H 15 or H 13 ) CDCl 3 ) ? 156.0 (s, low intensity, 5.44 (d, J = 10.5 Hz, 1H, H 6 ), 4.99 (dd, J = 11.8 Hz and J = 4.7 Hz, 1H, H 1 ), 3.95 (br m, 1H, OH) 0.53 (apparent q, J = 5.2 Hz, 1H, H 3' ); 13 C NMR (100 MHz, pp.75-76, 2003.
, 42 (apparent br t, J = 11.0 Hz, 1H, H 1' ), 3.30 (br m, 1H, OH), 1.88 (t, J = 1.2 Hz, 3H, H 13 or H 15, pp.4-7567
, J = 6.2 Hz and J = 5.6 Hz, 1H, H 3 ); 13 C NMR (100 MHz, CDCl 3 ) ? 163.7 (s, C 12 ), 143.7 (s, C 9 ) (s, C 5 or C 14 ), 132.0 (s, C 14 or C 5 ), pp.55-78
, CDCl 3 ) ? 7.30 (dd, J = 7.4 Hz and J = 1, 2008.
, J = 7.4 Hz and J = 1.0 Hz, 1H, pp.994900-994904
, 1.50 (s, 3H, H 15 or H 13 ), 1.45?1.35 (br m, 1H, H 3 ); 13 C NMR (100 MHz, DMSO-d 6 , 324K) ? 158.3 (s, C 12 ), 136.0 (s, C 5 or C 14
, 21 (dd, J = 10.1 Hz and J = 7.2 Hz, 1H, H 1667 (very br s, 1H, OH), 1.92 (d, J = 2.1 Hz, 3H, H 13 or H 15 ), 1.85 (br s, 3H, H 15 or H 13 CDCl 3 ) some methanolysis, work-up and purification by flash chromatography, C NMR (100 MHz) gave 149 mg (96%) of acetate 226 as a white solid, p.25
, CDCl 3 ) ? 7.16 (dd, J = 9.0 Hz and J = 313 (s, 3H, Hz and J = 5.2 Hz, 1H, H 10 ), 6.88 (ddd, J = 8.7 Hz, J = 7.8 Hz and J = 3.0 Hz, 1H, H 11 ), 6.55 (s, 1H, H 6 ), 4.35 (dd, J = 11.5 Hz and J = 3.0 Hz, 1H (apparent q, J = 5.2 Hz, 1H, H 3 ); 13 C NMR (100 MHz, CDCl 3 ) ? 169.9 (s, C 16 ), pp.714-715, 1020.
, 09 (s, 3H, H 18 ), 1.79 (s, 3H, (2R*,4R*,6S*)-11-Fluoro12-trien-8-yl acetate (229) Ozonolysis of 226 (138 mg, 0.475 mmol) in CH 2 Cl 2 (10 mL) at -78 °C, subsequent treatment with a solution of PPh 3 (187 mg, 0.712 mmol, CH 2 Cl 2 (2 mL) (rt, 2 h) and purification by flash chromatography, pp.4-06, 2004.
, 21 (s, 1H, H 6 ), 4.52 (br m, 1H, H 1 ), 4.25 (dd, J = 12.4 Hz and J = 2, 14 ), 2.10 (ddd, J = 9.4 Hz, J = 8.3 Hz and J = 6.6 Hz, 1H, H 4 ), 1.78 (m, 1H, pp.3-6, 1924.
, 13 C NMR (100 MHz, CDCl 3 ) ? 203.2 (s, C 5 ), 170.1 (s, C 13 ), 159.6 (s, 1 J C-F = 243 Hz, C 9 ), 152.8 (s, 4 J C-F = 3
, (m, 2H, H 9 ); 13 C NMR (100 MHz, CDCl 3 ) ? 192, m, 2H, H 8, pp.17-20
, 27 (apparent dq, J = 10.6 Hz and J = 1.5 Hz, 1H, H 13, p.92
, 87 (ddt, J = 16.9 Hz, J = 10.2 Hz and J = 6.6 Hz, 1H, H 18 or H 12, pp.82-87
, 00 (ddd, J = 17.3 Hz, J = 10.3 Hz and J = 7.2 Hz, 1H, H 14 ), 5.23 (dt, J = 17, 1H, H 15' ), 3.89 (m, 1H, H 1 ), 2.65 (dd, J = 16.8 Hz and J = 2.6 Hz, 1H, H 2 ), p.1458
, 44 (s, 3H, H 11 ), 1.43 (s, 3H, H 11' ), N-H and O-H protons cannot be unambiguously assigned; 13 C NMR (100 MHz, CDCl 3 ) ? 146.3 (s, C 10