Tetrafluoroboric acid → Hedione

HRID 323539

反応式

HRID 323539 の反応式
C[C@H]1P(C2C(P3[C@H](C)CC[C@H]3C)=CC=CC=2)[C@H](C)CC1.[O:21]=[C:22]1[CH2:26][CH2:25][C:24]([CH2:27][C:28]([O:30][CH3:31])=[O:29])=[C:23]1[CH2:32][CH2:33][CH2:34][CH2:35][CH3:36].[H+].[B-](F)(F)(F)F>C(Cl)Cl>[CH3:36][CH2:35][CH2:34][CH2:33][CH2:32][CH:23]1[C:22](=[O:21])[CH2:26][CH2:25][CH:24]1[CH2:27][C:28]([O:30][CH3:31])=[O:29]

参加物

5

反応物 3

HCID 28118Tetrafluoroboric acidHCID 906341-Cyclopentene-1-acetic acid, 3-oxo-2-pentyl-, methyl ester2 回HCID 2734551Methyl-duphos, (R,R)-

生成物 1

HCID 102861Hedione収率 99%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒2 回

実験手順

In a glovebox, into a 10 ml glass vial were placed 15.5 mg (0.0485 mmole) of [(COD)Ru(methylallyl)2], 14.9 mg (0.0485 mmole) of (R,R)-Me-DuPHOS and 250 μl of methyl 3-oxo-2-pentyl-1-cyclopentene-1-acetate (1.08 mmole). To this suspension was added 0.630 ml of a 0.081 M solution of titrated HBF4.etherate (0.049 mmole) in CH2Cl2 with stirring. This concentrated solution was stirred for 1.5 hours, after which 21.5 g (95.9 mmole) of methyl 3-oxo-2-pentyl-1-cyclopentene-1-acetate and 11.5 ml of CH2Cl2 were added. The resulting yellow solution was placed in a 75 ml autoclave, purged with hydrogen and pressurized to 90 bar of hydrogen. After 8 hours, the solution was exposed to air and passed through a column of silica gel to separate the catalyst. This gave a 99% yield of the desired Hedione® product with the following ratios of isomers: cis/trans=98/2; (+)-cis/(−)-cis=82.4/17.6, 64.8% ee.

後処理

  1. custompurged with hydrogen
  2. waitAfter 8 hours
  3. customto separate the catalyst

出典と根拠

ORDレコード
ord-4b6e3a2600fa42d392022af60fbf7df0
出典データセット
uspto-grants-2001_04
特許番号
US06214763B1

関連ノート

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