1,3-Bis(diphenylphosphino)propane → Methyl (R)-3-((tert-butoxycarbonyl)amino)-2,3-dihydro-1H-indene-5-carboxylate

HRID 1253638ノート

反応式

HRID 1253638 の反応式
Br[C:2]1[CH:10]=[C:9]2[C:5]([CH2:6][CH2:7][C@H:8]2[NH:11][C:12](=[O:18])[O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[CH:4][CH:3]=1.C1(P(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>CO.CS(C)=O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[C:14]([O:13][C:12]([NH:11][C@H:8]1[C:9]2[C:5](=[CH:4][CH:3]=[C:2]([C:12]([O:13][CH3:14])=[O:18])[CH:10]=2)[CH2:6][CH2:7]1)=[O:18])([CH3:17])([CH3:16])[CH3:15]

参加物

6

反応物 2

HCID 812191,3-Bis(diphenylphosphino)propaneHCID 59505686(R)-(6-Bromo-indan-1-yl)-carbamic acid tert-butyl ester

生成物 1

HCID 59505324Methyl (R)-3-((tert-butoxycarbonyl)amino)-2,3-dihydro-1H-indene-5-carboxylate収率 76%

試薬・触媒・溶媒 3

HCID 167845palladium(II) acetate触媒HCID 679Dimethyl Sulfoxide溶媒HCID 887Methanol溶媒

反応条件

温度
75 °C

実験手順

A solution of (R)-tert-butyl 6-bromo-2,3-dihydro-1H-inden-1-ylcarbamate (15.0 g, 48.07 mmol, 1.0 eq.) in a mixture of MeOH (200 ml) and DMSO (30 ml) was degassed with argon for 30 min followed by addition of palladium acetate (0.53 g, 2.40 mmol, 0.05 eq.), 1,3-bis(diphenylphosphino)propane (0.99 g, 2.40 mmol, 0.05 eq.) and TEA (20 ml, 144.21 mmol, 3.0 eq.). The reaction mixture was then sealed in an autoclave using CO pressure (80 psi) and heated at 75° C. for 16 h. The mixture was evaporated to dryness, diluted with water (150 ml) and extracted with ethyl acetate (2×300 ml). The combined organic layers were washed with brine (100 ml), dried over anhydrous Na2SO4 and evaporated to give the crude product which was purified by column chromatography (silica gel; 5% ethyl acetate/hexanes) to yield the desired product as a white solid. Yield: 76% (10.6 g, 36.43 mmol).

後処理

  1. customwas degassed with argon for 30 min
  2. customThe reaction mixture was then sealed in an autoclave
  3. customThe mixture was evaporated to dryness
  4. additiondiluted with water (150 ml)
  5. extractionextracted with ethyl acetate (2×300 ml)
  6. washThe combined organic layers were washed with brine (100 ml)
  7. dry with materialdried over anhydrous Na2SO4
  8. customevaporated
  9. customto give the crude product which
  10. customwas purified by column chromatography (silica gel; 5% ethyl acetate/hexanes)

出典と根拠

ORDレコード
ord-9de0ddcf505e49e981e40749a02d676e
出典データセット
uspto-grants-2013_06
特許番号
US08455475B2

反応ノート

読み込み中…