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

HRID 471045

Reaktionsgleichung

Reaktionsgleichung von HRID 471045
FC(F)(F)C(O)=O.[CH:8]([C:11]1[S:12][CH:13]=[C:14]([C:16]([N:18]2[CH2:23][C:22]3([CH2:28][CH2:27][NH:26][CH2:25][CH2:24]3)[O:21][CH2:20][CH2:19]2)=[O:17])[N:15]=1)([CH3:10])[CH3:9].[Si:29]([O:36][CH2:37][CH2:38][C:39]1[CH:40]=[C:41]([CH:44]=O)[S:42][CH:43]=1)([C:32]([CH3:35])([CH3:34])[CH3:33])([CH3:31])[CH3:30].[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:29]([O:36][CH2:37][CH2:38][C:39]1[CH:40]=[C:41]([CH2:44][N:26]2[CH2:25][CH2:24][C:22]3([O:21][CH2:20][CH2:19][N:18]([C:16]([C:14]4[N:15]=[C:11]([CH:8]([CH3:10])[CH3:9])[S:12][CH:13]=4)=[O:17])[CH2:23]3)[CH2:28][CH2:27]2)[S:42][CH:43]=1)([C:32]([CH3:33])([CH3:35])[CH3:34])([CH3:31])[CH3:30]

Komponenten

8

Edukt 4

HCID 5049666Sodium triacetoxyborohydrideHCID 579889073-(2-(Tert-butyldimethylsilyloxy)ethyl)thiophene-2-carbaldehydeHCID 579891104-(2-(Tert-butyldimethylsilyloxy)ethyl)thiophene-2-carbaldehydeHCID 66964182(2-Isopropylthiazol-4-yl)(1-oxa-4,9-diazaspiro[5.5]undecan-4-yl)methanone trifluoroacetate

Produkt 1

HCID 57989092(9-((4-(2-(tert-Butyldimethylsilyloxy)ethyl)thiophen-2-yl)methyl)-1-oxa-4,9-diazaspiro[5.5]undecan-4-yl)(2-isopropylthiazol-4-yl)methanone

Reagenzien, Katalysatoren, Lösungsmittel 3

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

Versuchsvorschrift

(2-Isopropylthiazol-4-yl)(1-oxa-4,9-diazaspiro[5.5]undecan-4-yl)methanone trifluoroacetate (example 22, step b) (0.50 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) (0.40 g) and AcOH (0.085 mL) in N-methyl-2-pyrrolidinone (6 mL). After 5 min, sodium triacetoxyborohydride (0.48 g) was added. After 16 h water was added and the mixture was 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, 20:80:5 separated the two isomeric products and gave the subtitled compound as a gum. Yield 0.27 g.

Aufarbeitung

  1. extractionthe mixture was 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, 20:80:5 separated the two isomeric products

Quellen und Nachweise

ORD-Eintrag
ord-bcbef4bc932c406194528b4cc181e6ac
Quelldatensatz
uspto-grants-2014_01
Patentnummer
US08629271B2

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