Allyltributylstannane → 4-(2-allyl-4-(trifluoromethyl)phenyl)-N-(4-methoxybenzyl)-N-(thiazol-2-yl)-3,4-dihydro-2H-benzo[b][1,4]oxazine-7-sulfonamide

HRID 528595Notes

Reaction equation

HRID 528595 reaction equation
Br[C:2]1[CH:7]=[C:6]([C:8]([F:11])([F:10])[F:9])[CH:5]=[CH:4][C:3]=1[N:12]1[CH2:17][CH2:16][O:15][C:14]2[CH:18]=[C:19]([S:22]([N:25]([CH2:31][C:32]3[CH:37]=[CH:36][C:35]([O:38][CH3:39])=[CH:34][CH:33]=3)[C:26]3[S:27][CH:28]=[CH:29][N:30]=3)(=[O:24])=[O:23])[CH:20]=[CH:21][C:13]1=2.[CH2:40]([Sn](CCCC)(CCCC)CCCC)[CH:41]=[CH2:42]>CN(C=O)C.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH2:42]([C:2]1[CH:7]=[C:6]([C:8]([F:11])([F:10])[F:9])[CH:5]=[CH:4][C:3]=1[N:12]1[CH2:17][CH2:16][O:15][C:14]2[CH:18]=[C:19]([S:22]([N:25]([CH2:31][C:32]3[CH:37]=[CH:36][C:35]([O:38][CH3:39])=[CH:34][CH:33]=3)[C:26]3[S:27][CH:28]=[CH:29][N:30]=3)(=[O:24])=[O:23])[CH:20]=[CH:21][C:13]1=2)[CH:41]=[CH2:40]

Participants

5

Reactant 2

HCID 90628AllyltributylstannaneHCID 897614134-(2-bromo-4-(trifluoromethyl)phenyl)-N-(4-methoxybenzyl)-N-(thiazol-2-yl)-3,4-dihydro-2H-benzo[b][1,4]oxazine-7-sulfonamide

Product 1

HCID 897620874-(2-allyl-4-(trifluoromethyl)phenyl)-N-(4-methoxybenzyl)-N-(thiazol-2-yl)-3,4-dihydro-2H-benzo[b][1,4]oxazine-7-sulfonamideYield 96%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
100 °C

Procedure

A reaction vial was charged with 4-(2-bromo-4-(trifluoromethyl)phenyl)-N-(4-methoxybenzyl)-N-(thiazol-2-yl)-3,4-dihydro-2H-benzo[b][1,4]oxazine-7-sulfonamide (EXAMPLE 53, Step 1; 0.347 g, 0.542 mmol) and Pd(PPh3)4 (0.031 g, 0.027 mmol), and then diluted with DMF (1.084 ml). After purging with nitrogen, allyltributyltin (0.202 ml, 0.650 mmol) was added and the reaction was heated to 100° C. for 30 minutes until completion. The reaction was concentrated in vacuo and purified via silica-gel chromatography (12-g RediSep Gold column), eluting with 0-30% ethyl acetate in heptanes) to yield 4-(2-allyl-4-(trifluoromethyl)phenyl)-N-(4-methoxybenzyl)-N-(thiazol-2-yl)-3,4-dihydro-2H-benzo[b][1,4]oxazine-7-sulfonamide (0.312 g, 0.519 mmol, 96% yield) as a yellow oil. m/z (ESI) 602.1 (M+H)+.

Workup

  1. customA reaction
  2. additionwas added
  3. concentrationThe reaction was concentrated in vacuo
  4. custompurified via silica-gel chromatography (12-g RediSep Gold column)
  5. washeluting with 0-30% ethyl acetate in heptanes)

Sources & evidence

ORD record
ord-db47ff3223b546f9b0a044767b21f129
Source dataset
uspto-grants-2016_05
Patent number
US09346798B2

Reaction notes

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