Triphenylphosphine → ethyl 5-(4-((4-(5-amino-1-(tert-butoxycarbonyl)-4-cyano-1H-pyrazol-3-yl)phenoxy)methyl)phenyl)-2-(8-(benzo[d]thiazol-2-yl((2-(trimethylsilyl)ethoxy)methyl)carbamoyl)-3,4-dihydroisoquinolin-2(1H)-yl)thiazole-4-carboxylate

HRID 1518294Notes

Reaction equation

HRID 1518294 reaction equation
[S:1]1[C:5]2[CH:6]=[CH:7][CH:8]=[CH:9][C:4]=2[N:3]=[C:2]1[N:10]([CH2:41][O:42][CH2:43][CH2:44][Si:45]([CH3:48])([CH3:47])[CH3:46])[C:11]([C:13]1[CH:14]=[CH:15][CH:16]=[C:17]2[C:22]=1[CH2:21][N:20]([C:23]1[S:24][C:25]([C:33]3[CH:38]=[CH:37][C:36]([CH2:39][OH:40])=[CH:35][CH:34]=3)=[C:26]([C:28]([O:30][CH2:31][CH3:32])=[O:29])[N:27]=1)[CH2:19][CH2:18]2)=[O:12].C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[NH2:68][C:69]1[N:73]([C:74]([O:76][C:77]([CH3:80])([CH3:79])[CH3:78])=[O:75])[N:72]=[C:71]([C:81]2[CH:86]=[CH:85][C:84](O)=[CH:83][CH:82]=2)[C:70]=1[C:88]#[N:89].C1C=CC(COC(/N=N/C(OCC2C=CC=CC=2)=O)=O)=CC=1>C1COCC1>[NH2:68][C:69]1[N:73]([C:74]([O:76][C:77]([CH3:80])([CH3:79])[CH3:78])=[O:75])[N:72]=[C:71]([C:81]2[CH:86]=[CH:85][C:84]([O:40][CH2:39][C:36]3[CH:35]=[CH:34][C:33]([C:25]4[S:24][C:23]([N:20]5[CH2:19][CH2:18][C:17]6[C:22](=[C:13]([C:11](=[O:12])[N:10]([C:2]7[S:1][C:5]8[CH:6]=[CH:7][CH:8]=[CH:9][C:4]=8[N:3]=7)[CH2:41][O:42][CH2:43][CH2:44][Si:45]([CH3:47])([CH3:46])[CH3:48])[CH:14]=[CH:15][CH:16]=6)[CH2:21]5)=[N:27][C:26]=4[C:28]([O:30][CH2:31][CH3:32])=[O:29])=[CH:38][CH:37]=3)=[CH:83][CH:82]=2)[C:70]=1[C:88]#[N:89]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 5387121Dibenzyl azodicarboxylateHCID 59447480ethyl 2-(8-(benzo[d]thiazol-2-yl((2-(trimethylsilyl)ethoxy)methyl)carbamoyl)-3,4-dihydroisoquinolin-2(1H)-yl)-5-(4-(hydroxymethyl)phenyl)thiazole-4-carboxylateHCID 136027725tert-butyl 5-amino-4-cyano-3-(4-hydroxyphenyl)-1H-pyrazole-1-carboxylate

Product 1

HCID 59447596ethyl 5-(4-((4-(5-amino-1-(tert-butoxycarbonyl)-4-cyano-1H-pyrazol-3-yl)phenoxy)methyl)phenyl)-2-(8-(benzo[d]thiazol-2-yl((2-(trimethylsilyl)ethoxy)methyl)carbamoyl)-3,4-dihydroisoquinolin-2(1H)-yl)thiazole-4-carboxylateYield 601%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

A mixture of compound 34D (0.14 g, 0.2 mmol), PPh3 (0.079 g, 0.3 mmol), and compound 31F (0.066 g, 0.022 mmol) was dissolved in THF (3 mL). The solution was cooled to 0° C. To this solution was added DBAD. The reaction mixture was stirred at rt for 2 hours. The solvent was removed, and the residue was purified by flash column chromatography on silica gel eluting with 2:1/hexanes:EtOAc to afford 0.13 g of the title compound as a mixture of two inseparable isomers. MS (ESI(+)): m/z 982 (M+NH4—H2O).

Workup

  1. customThe solvent was removed
  2. customthe residue was purified by flash column chromatography on silica gel eluting with 2:1/hexanes

Sources & evidence

ORD record
ord-cd5eff0794df4d0393718ae186866d3f
Source dataset
uspto-grants-2012_07
Patent number
US08232273B2

Reaction notes

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