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Trifluoroacetic anhydride → (S)-tert-butyl 2-((tert-butyldiphenylsilyloxy)methyl)-2,3-dihydro-1H-pyrrole-1-carboxylate

HRID 1471113
ノート
印刷プレビュー

反応式

HRID 1471113 の反応式
[Si:1]([O:18][CH2:19][C@@H:20]1[CH2:24][CH2:23][C:22](=O)[N:21]1[C:26]([O:28][C:29]([CH3:32])([CH3:31])[CH3:30])=[O:27])([C:14]([CH3:17])([CH3:16])[CH3:15])([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C([BH-](CC)CC)C.[Li+].CCN(C(C)C)C(C)C.FC(F)(F)C(OC(=O)C(F)(F)F)=O>CN(C1C=CN=CC=1)C.C1(C)C=CC=CC=1>[Si:1]([O:18][CH2:19][C@@H:20]1[CH2:24][CH:23]=[CH:22][N:21]1[C:26]([O:28][C:29]([CH3:32])([CH3:31])[CH3:30])=[O:27])([C:14]([CH3:16])([CH3:17])[CH3:15])([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1
参加物実験手順後処理出典と根拠反応ノート

参加物

7

反応物 4

HCID 9845Trifluoroacetic anhydrideHCID 81531DiisopropylethylamineHCID 11762195(S)-tert-Butyl 2-(((tert-butyldiphenylsilyl)oxy)methyl)-5-oxopyrrolidine-1-carboxylateHCID 23664628Lithiumtriethylborohydride

生成物 1

HCID 13008516(S)-tert-butyl 2-((tert-butyldiphenylsilyloxy)methyl)-2,3-dihydro-1H-pyrrole-1-carboxylate収率 82%

試薬・触媒・溶媒 2

HCID 142844-(Dimethylamino)pyridine触媒HCID 1140Toluene溶媒

実験手順

A three-necked flask equipped with a thermometer and a nitrogen inlet was charged with (S)-tert-butyl 2-((tert-butyldiphenylsilyloxy)methyl)-5-oxopyrrolidine-1-carboxylate (10.05 g, 22.16 mmol) and toluene (36 mL) and lowered into −55° C. cooling bath. When the internal temperature of the mixture reached −50° C., lithium triethylborohydride (23 mL of 1.0 M/THF, 23 mmol) was added dropwise over 30 min and the mixture stirred for 35 min while maintaining the internal temperature between −50° C. and −45° C. Hunig's base (16.5 mL, 94 mmol) was added dropwise over 10 min. Then, DMAP (34 mg, 0.278 mmol) was added in one batch, followed by the addition of trifluoroacetic anhydride (3.6 mL, 25.5 mmol) over 15 min, while maintaining the internal temperature between −50° C. and −45° C. The bath was removed 10 min later and the reaction mixture was stirred for 14 h while allowing it to rise to ambient temperature. The reaction mixture was diluted with toluene (15 mL), cooled with an ice-water bath and treated slowly with water (55 mL) over 5 min. The phases were separated and the organic layer washed with water (50 mL, 2×) and concentrated in vacuo. The crude material was purified by flash chromatography (silica gel; 5% EtOAc/hexanes) to afford (S)-tert-butyl 2-((tert-butyldiphenylsilyloxy)methyl)-2,3-dihydro-1H-pyrrole-1-carboxylate (7.947 g, 82% yield) as a colorless viscous oil. LC/MS: [M+Na]+=460.19. Rt=2.41 min under the following HPLC conditions: Solvent gradient from 100% A:0% B to 0% A:100% B (A=0.1% TFA in 1:9 MeOH/water; B=0.1% TFA in 9:1 MeOH/water) over 2 min and hold for 1 min; detection at 220 nm; PHENOMENEX®Luna 3.0×50 mm S10 column. 1H NMR (400 MHz, DMSO-d6) δ ppm 7.62-7.58 (m, 4H), 7.49-7.40 (m, 6H), 6.47 (br s, 1H), 5.07/5.01 (overlapping br d, 1H), 4.18 (br s, 1H), 3.89 (br s, 0.5H), 3.69 (br s, 1.5H), 2.90-2.58 (br m, 2H), 1.40/1.26 (overlapping br s, 9H), 0.98 (s, 9H).

後処理

  1. customA three-necked flask equipped with a thermometer and a nitrogen inlet
  2. customlowered into −55° C.
  3. temperaturecooling bath
  4. customreached −50° C.
  5. temperaturewhile maintaining the internal temperature between −50° C. and −45° C
  6. temperaturewhile maintaining the internal temperature between −50° C. and −45° C
  7. customThe bath was removed 10 min later
  8. stirringthe reaction mixture was stirred for 14 h
  9. customto rise to ambient temperature
  10. additionThe reaction mixture was diluted with toluene (15 mL)
  11. temperaturecooled with an ice-water bath
  12. additiontreated slowly with water (55 mL) over 5 min
  13. customThe phases were separated
  14. washthe organic layer washed with water (50 mL, 2×)
  15. concentrationconcentrated in vacuo
  16. customThe crude material was purified by flash chromatography (silica gel; 5% EtOAc/hexanes)

出典と根拠

ORDレコード
ord-ccaaef98a4724b29bcb76b28cb489f10
出典データセット
uspto-grants-2015_04
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US09006455B2

反応ノート

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