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tert-Butyl methyl ether → (S)-1-{(3aS,7E,7aR)-7-(bromomethylene)-3a,4,5,6,7,7a-hexahydro-3a-methyl-1H-indene-3-yl}ethanol

HRID 1922640
ノート
印刷プレビュー

反応式

HRID 1922640 の反応式
[CH3:1]OC(C)(C)C.C[Zn]C.[Br:10]/[CH:11]=[C:12]1/[C@H:13]2[C@:17]([CH3:21])([CH2:18][CH2:19][CH2:20]/1)[C:16]([CH:22]=[O:23])=[CH:15][CH2:14]2>C(O[Ti](OC(C)C)(OC(C)C)OC(C)C)(C)C.[C@@H]1(NS(C(F)(F)F)(=O)=O)CCCC[C@H]1NS(C(F)(F)F)(=O)=O.C(OCC)(=O)C>[Br:10]/[CH:11]=[C:12]1\[CH2:20][CH2:19][CH2:18][C@@:17]2([CH3:21])[C@H:13]\1[CH2:14][CH:15]=[C:16]2[C@@H:22]([OH:23])[CH3:1]
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

7

反応物 3

HCID 15413tert-Butyl methyl etherHCID 59456515(3aR,4E,7aS)-4-(bromomethylene)-3a,4,5,6,7,7a-hexahydro-7a-methyl-3H-indene-1-carbaldehyde2 回HCID 178477796HCID 178477796、化合物

生成物 1

HCID 59456520(S)-1-{(3aS,7E,7aR)-7-(bromomethylene)-3a,4,5,6,7,7a-hexahydro-3a-methyl-1H-indene-3-yl}ethanol収率 100%

試薬・触媒・溶媒 3

HCID 11090167
(1R)-trans-N,N'-1,2-Cyclohexanediylbis(1,1,1-trifluoromethanesulfonamide)
触媒
HCID 178460666HCID 178460666、化合物触媒
HCID 8857Ethyl Acetate溶媒

反応条件

温度
50 °C

実験手順

(1R)-trans-N,N′-1,2-cyclohexanediylbis(1,1,1-trifluoromethanesulfonamide) (2.3 mg, 0.006 mmol) was placed in a reaction vessel. After replacing the atmosphere with nitrogen, t-butyl methyl ether (0.03 ml) was added thereto and dissolved. To the solution, tetraisopropoxy titanium (0.0177 ml, 0.06 mmol) was added at room temperature, and the resulting mixture was heated at 50° C. for 30 minutes. After cooling to room temperature, dimethylzinc (1.0 M in heptane, 0.12 ml, 0.12 mmol) was added thereto. The obtained reaction mixture was added to (3aR,4E,7aS)-4-(bromomethylene)-3a,4,5,6,7,7a-hexahydro-7a-methyl-3H-indene-1-carbaldehyde (Compound 29: 15.3 mg, 0.06 mmol). After stirring the reaction solution at room temperature for 1 hour, ethyl acetate (30 ml) was added thereto, and the resulting mixture was washed with 2N hydrochloric acid, saturated brine and with saturated aqueous sodium hydrogen carbonate solution, respectively. The organic layer was dried over sodium sulfate, and the solvent was evaporated to obtain the reaction mixture. The reaction mixture was purified by preparative TCL to obtain (S)-1-{(3aS,7E,7aR)-7-(bromomethylene)-3a,4,5,6,7,7a-hexahydro-3a-methyl-1H-indene-3-yl}ethanol (18.4 mg, 100%). The spectrum data thereof agreed with the data described in Example 4.

後処理

  1. additionwas added
  2. dissolutiondissolved
  3. temperatureAfter cooling to room temperature
  4. customThe obtained reaction mixture
  5. washthe resulting mixture was washed with 2N hydrochloric acid, saturated brine and with saturated aqueous sodium hydrogen carbonate solution
  6. dry with materialThe organic layer was dried over sodium sulfate
  7. customthe solvent was evaporated
  8. customto obtain the reaction mixture
  9. customThe reaction mixture was purified by preparative TCL

出典と根拠

ORDレコード
ord-3695cd263fa04fa5bcbd7f6e0258f1a9
出典データセット
uspto-grants-2012_05
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US08173824B2

反応ノート

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