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

Reaction equation

HRID 471026 reaction equation
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]

Participants

8

Reactant 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

Product 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

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 962WaterSolventHCID 13387N-methyl-2-pyrrolidoneSolvent

Procedure

(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.

Workup

  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

Sources & evidence

ORD record
ord-70db08011b034097b8b32817ddbc77a0
Source dataset
uspto-grants-2014_01
Patent number
US08629271B2

Linked notes

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