Sodium triacetoxyborohydride → (9-((4-(2-(tert-Butyldimethylsilyloxy)ethyl)thiophen-2-yl)methyl)-1-oxa-4,9-diazaspiro[5.5]undecan-4-yl)(5-methylthiophen-2-yl)methanone

HRID 471026

Reaktionsgleichung

Reaktionsgleichung von HRID 471026
FC(F)(F)C(O)=O.[CH3:8][C:9]1[S:13][C:12]([C:14]([N:16]2[CH2:21][C:20]3([CH2:26][CH2:25][NH:24][CH2:23][CH2:22]3)[O:19][CH2:18][CH2:17]2)=[O:15])=[CH:11][CH:10]=1.[Si:27]([O:34][CH2:35][CH2:36][C:37]1[CH:38]=[C:39]([CH:42]=O)[S:40][CH:41]=1)([C:30]([CH3:33])([CH3:32])[CH3:31])([CH3:29])[CH3:28].[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:27]([O:34][CH2:35][CH2:36][C:37]1[CH:38]=[C:39]([CH2:42][N:24]2[CH2:25][CH2:26][C:20]3([O:19][CH2:18][CH2:17][N:16]([C:14]([C:12]4[S:13][C:9]([CH3:8])=[CH:10][CH:11]=4)=[O:15])[CH2:21]3)[CH2:22][CH2:23]2)[S:40][CH:41]=1)([C:30]([CH3:31])([CH3:33])[CH3:32])([CH3:29])[CH3:28]

Komponenten

8

Edukt 4

HCID 5049666Sodium triacetoxyborohydrideHCID 579889073-(2-(Tert-butyldimethylsilyloxy)ethyl)thiophene-2-carbaldehydeHCID 579891104-(2-(Tert-butyldimethylsilyloxy)ethyl)thiophene-2-carbaldehydeHCID 67292300(5-Methylthiophen-2-yl)(1-oxa-4,9-diazaspiro[5.5]undecan-4-yl)methanone trifluoroacetate

Produkt 1

HCID 57989318(9-((4-(2-(tert-Butyldimethylsilyloxy)ethyl)thiophen-2-yl)methyl)-1-oxa-4,9-diazaspiro[5.5]undecan-4-yl)(5-methylthiophen-2-yl)methanone

Reagenzien, Katalysatoren, Lösungsmittel 3

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

Versuchsvorschrift

(5-Methylthiophen-2-yl)(1-oxa-4,9-diazaspiro[5.5]undecan-4-yl)methanone trifluoroacetate (example 9, step b) (0.230 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) (0.20 g) and AcOH (0.033 mL) in N-methyl-2-pyrrolidinone (3 mL). After 5 min, sodium triacetoxyborohydride (0.35 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 20:80:5 ethyl acetate:isohexane:triethylamine, separated the two isomeric products and gave the subtitled compound as a gum. Yield 0.21 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 20:80:5 ethyl acetate
  6. customisohexane:triethylamine, separated the two isomeric products

Quellen und Nachweise

ORD-Eintrag
ord-70db08011b034097b8b32817ddbc77a0
Quelldatensatz
uspto-grants-2014_01
Patentnummer
US08629271B2

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