Pentane → {4-[(Bicyclo[2.2.1]hept-5-en-2-yl)methoxy]phenyl}(diphenyl)phosphane

HRID 2035317ノート

反応式

HRID 2035317 の反応式
I[C:2]1[CH:7]=[CH:6][C:5]([O:8][CH2:9][CH:10]2[CH2:15][CH:14]3[CH2:16][CH:11]2[CH:12]=[CH:13]3)=[CH:4][CH:3]=1.CCCCC.[C:22]1([P:28]([C:33]2[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=2)[Si](C)(C)C)[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1>C1(C)C=CC=CC=1.CC#N.CC#N.Cl[Pd]Cl>[CH:11]12[CH2:16][CH:14]([CH:13]=[CH:12]1)[CH2:15][CH:10]2[CH2:9][O:8][C:5]1[CH:6]=[CH:7][C:2]([P:28]([C:33]2[CH:34]=[CH:35][CH:36]=[CH:37][CH:38]=2)[C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)=[CH:3][CH:4]=1

参加物

6

反応物 3

HCID 8003PentaneHCID 140190Diphenyl(trimethylsilyl)phosphineHCID 219893005-[(4-Iodophenoxy)methyl]bicyclo[2.2.1]hept-2-ene

生成物 1

HCID 21989303{4-[(Bicyclo[2.2.1]hept-5-en-2-yl)methoxy]phenyl}(diphenyl)phosphane収率 14.7%

試薬・触媒・溶媒 2

HCID 6093782Bis(acetonitrile)dichloropalladium触媒HCID 1140Toluene溶媒

反応条件

温度
70 °C

実験手順

Bis(acetonitrile)dichloropalladium(II) (1 mmol) was placed in a Schlenk flask, stoppered with a septum and evacuated and purged with nitrogen three times. To this flask was then added a solution of 8 (0.038 mol) in 100 mL of anhydrous toluene and 9.6 g of diphenyl(trimethylsilyl)phosphine. The resulting deep purple solution was heated at 70° C. overnight, then cooled to room temperature and the solvent evaporated under reduced pressure. The residue was chromatographed on a column of silica gel using first hexane and then 9:1 hexane ethyl acetate as eluent to collect the product. After evaporation of the solvent, the product 9 (10 g), a mixture of endo and exo isomers, was obtained as white gummy material. Addition of 50 mL of hot pentane to this compound resulted in the separation of white crystalline compound (2.1 g). 1H NMR (500 MHz, 25° C., CDCl3): δ (endo isomer, ˜85%) 7.30 (m, 12H, Ar—H), 6.88 (m, 2H, Ar—H), 6.18 (m, 1H, olefinic), 5.98 (m, 1H, olefinic), 3.72 (m, 1H, nor-CH2), 3.57 (m 1H, nor-CH2), 3.04 (br s 1H), 2.88 (br s, 1H), 2.53 (m, 1H), 1.92 (m, 1H), 1.51 (d, |J|=8.0 Hz), 1.32 (d, |J|=8.2 Hz, 1H), 0.65 (m, 1H); (exo isomer, partial) 6.92 (m, 2H, Ar—H), 4.05 (m, 1H), 3.88 (m, 1H). 31P {1H} NMR (200 MHz, 25° C., CDCl3): δ −6.57

後処理

  1. customevacuated
  2. custompurged with nitrogen three times
  3. temperaturecooled to room temperature
  4. customthe solvent evaporated under reduced pressure
  5. customThe residue was chromatographed on a column of silica gel using first hexane
  6. custom9:1 hexane ethyl acetate as eluent to collect the product
  7. customAfter evaporation of the solvent
  8. additionthe product 9 (10 g), a mixture of endo and exo isomers
  9. customwas obtained as white gummy material

出典と根拠

ORDレコード
ord-4a5cb7caa99746bfb61f14b73d2a214b
出典データセット
uspto-grants-2013_11
特許番号
US08574680B2

反応ノート

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