Sodium triacetoxyborohydride → 1-(9-((4-(2-(tert-Butyldimethylsilyloxy)ethyl)thiophen-2-yl)methyl)-1-oxa-4,9-diazaspiro[5.5]undecan-4-yl)-2,2,2-trifluoroethanone

HRID 471069

Reaktionsgleichung

Reaktionsgleichung von HRID 471069
FC(F)(F)C(O)=O.[F:8][C:9]([F:24])([F:23])[C:10]([N:12]1[CH2:17][C:16]2([CH2:22][CH2:21][NH:20][CH2:19][CH2:18]2)[O:15][CH2:14][CH2:13]1)=[O:11].[Si:25]([O:32][CH2:33][CH2:34][C:35]1[CH:36]=[C:37]([CH:40]=O)[S:38][CH:39]=1)([C:28]([CH3:31])([CH3:30])[CH3:29])([CH3:27])[CH3:26].[Si](OCCC1C=CSC=1C=O)(C(C)(C)C)(C)C.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+]>CN1CCCC1=O.O.CC(O)=O>[Si:25]([O:32][CH2:33][CH2:34][C:35]1[CH:36]=[C:37]([CH2:40][N:20]2[CH2:21][CH2:22][C:16]3([O:15][CH2:14][CH2:13][N:12]([C:10](=[O:11])[C:9]([F:8])([F:23])[F:24])[CH2:17]3)[CH2:18][CH2:19]2)[S:38][CH:39]=1)([C:28]([CH3:29])([CH3:31])[CH3:30])([CH3:27])[CH3:26]

Komponenten

8

Edukt 4

HCID 5049666Sodium triacetoxyborohydrideHCID 579889073-(2-(Tert-butyldimethylsilyloxy)ethyl)thiophene-2-carbaldehydeHCID 579891104-(2-(Tert-butyldimethylsilyloxy)ethyl)thiophene-2-carbaldehydeHCID 866367502,2,2-Trifluoro-1-(1-oxa-4,9-diazaspiro[5.5]undecan-4-yl)ethanone trifluoroacetate

Produkt 1

HCID 579892241-(9-((4-(2-(tert-Butyldimethylsilyloxy)ethyl)thiophen-2-yl)methyl)-1-oxa-4,9-diazaspiro[5.5]undecan-4-yl)-2,2,2-trifluoroethanone

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 176Acetic AcidLösungsmittelHCID 962WaterLösungsmittelHCID 13387N-methyl-2-pyrrolidoneLösungsmittel

Versuchsvorschrift

2,2,2-Trifluoro-1-(1-oxa-4,9-diazaspiro[5.5]undecan-4-yl)ethanone trifluoroacetate (example 12, step d) (1.084 g) was added to a stirred solution of a 4:1 mixture of 4-(2-(tert-butyldimethylsilyloxy)ethyl)thiophene-2-carbaldehyde and 3-(2-(tert-butyldimethylsilyloxy)ethyl)thiophene-2-carbaldehyde (example 27, step b) (1.0 g), and AcOH (0.16 mL) in N-methyl-2-pyrrolidinone (15 mL). After 5 min, sodium triacetoxyborohydride (1.57 g) was added. After 16 h water was added and the mixture extracted with ethyl acetate. The ethyl acetate layer was washed three times with water and evaporated in vacuo. Purification by silica gel chromatography eluting with ethyl acetate:isohexane:triethylamine, 1:20:1 separated the two isomeric products and gave the subtitled compound as an oil. Yield 1.04 g.

Aufarbeitung

  1. extractionthe mixture extracted with ethyl acetate
  2. washThe ethyl acetate layer was washed three times with water
  3. customevaporated in vacuo
  4. customPurification by silica gel chromatography
  5. washeluting with ethyl acetate
  6. customisohexane:triethylamine, 1:20:1 separated the two isomeric products

Quellen und Nachweise

ORD-Eintrag
ord-efde6bf7cc3344aeaf845b5089f0d163
Quelldatensatz
uspto-grants-2014_01
Patentnummer
US08629271B2

Verknüpfte Notizen

Wird geladen…