Ethyl diazoacetate → Ethyl N-{1-[2-(6-cyano-3-oxo-2,3-dihydro-4H-1,4-benzoxazin-4-yl)ethyl]piperidin-4-yl}-N-[(2E)-3-(2,5-difluorophenyl)prop-2-en-1-yl]glycinate

HRID 255261Notes

Reaction equation

HRID 255261 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([F:8])=[CH:4][C:3]=1/[CH:9]=[CH:10]/[CH2:11][NH:12][CH:13]1[CH2:18][CH2:17][N:16]([CH2:19][CH2:20][N:21]2[C:26]3[CH:27]=[C:28]([C:31]#[N:32])[CH:29]=[CH:30][C:25]=3[O:24][CH2:23][C:22]2=[O:33])[CH2:15][CH2:14]1.[N+](=[CH:36][C:37]([O:39][CH2:40][CH3:41])=[O:38])=[N-]>ClCCl.C([O-])(=O)C.[Rh+2].C([O-])(=O)C>[C:31]([C:28]1[CH:29]=[CH:30][C:25]2[O:24][CH2:23][C:22](=[O:33])[N:21]([CH2:20][CH2:19][N:16]3[CH2:17][CH2:18][CH:13]([N:12]([CH2:11]/[CH:10]=[CH:9]/[C:3]4[CH:4]=[C:5]([F:8])[CH:6]=[CH:7][C:2]=4[F:1])[CH2:36][C:37]([O:39][CH2:40][CH3:41])=[O:38])[CH2:14][CH2:15]3)[C:26]=2[CH:27]=1)#[N:32]

Participants

5

Reactant 2

HCID 12192Ethyl diazoacetateHCID 119832164-[2-(4-{[(2E)-3-(2,5-difluorophenyl)prop-2-en-1-yl]amino}piperidin-1-yl)ethyl]-3-oxo-3,4-dihydro-2H-1,4-benzoxazine-6-carbonitrile

Product 1

HCID 15982020Ethyl N-{1-[2-(6-cyano-3-oxo-2,3-dihydro-4H-1,4-benzoxazin-4-yl)ethyl]piperidin-4-yl}-N-[(2E)-3-(2,5-difluorophenyl)prop-2-en-1-yl]glycinateYield 5%

Reagents, catalysts & solvents 2

HCID 21674Acetic acid, rhodium(2+) saltCatalystHCID 6344DichloromethaneSolvent

Procedure

To a mixture of 4-[2-(4-{[(2E)-3-(2,5-difluorophenyl)prop-2-en-1-yl]amino}piperidin-1-yl)ethyl]-3-oxo-3,4-dihydro-2H-1,4-benzoxazine-6-carbonitrile (Example 37) (120 mg, 0.265 mmol) and ethyl diazoacetate (0.09 mL) in dichloromethane (5 ml) was added rhodium(II) acetate (4 mg, 0.009 mmol) at room temperature. After 72 hrs, the product was concentrated and purified by preparative TLC to give 6.7 mg of product (5%).

Workup

  1. concentrationthe product was concentrated
  2. custompurified by preparative TLC

Sources & evidence

ORD record
ord-1be2c0b6f4ec4937b5db80d7e5f1e408
Source dataset
uspto-grants-2011_01
Patent number
US07875715B2

Reaction notes

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