Cesium carbonate → Methyl O-(3'-amino-1,1'-biphenyl-3-yl)-N-triphenylmethyl-L-serinate

HRID 1265219Notes

Reaction equation

HRID 1265219 reaction equation
C1([As](C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.Br[C:21]1[CH:22]=[C:23]([O:27][CH2:28][C@@H:29]([C:50]([O:52][CH3:53])=[O:51])[NH:30][C:31]([C:44]2[CH:49]=[CH:48][CH:47]=[CH:46][CH:45]=2)([C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=2)[C:32]2[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=2)[CH:24]=[CH:25][CH:26]=1.S(O)(O)(=O)=O.[NH2:59][C:60]1[CH:61]=[C:62](B(O)O)[CH:63]=[CH:64][CH:65]=1.NC1C=C(B(O)O)C=CC=1.C(=O)([O-])[O-].[Cs+].[Cs+]>COCCOC.O.C1(C)C=CC=CC=1>[NH2:59][C:60]1[CH:65]=[C:64]([C:21]2[CH:26]=[CH:25][CH:24]=[C:23]([O:27][CH2:28][C@@H:29]([C:50]([O:52][CH3:53])=[O:51])[NH:30][C:31]([C:38]3[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=3)([C:44]3[CH:49]=[CH:48][CH:47]=[CH:46][CH:45]=3)[C:32]3[CH:33]=[CH:34][CH:35]=[CH:36][CH:37]=3)[CH:22]=2)[CH:63]=[CH:62][CH:61]=1

Participants

8

Reactant 4

HCID 10796Cesium carbonateHCID 11773TriphenylarsineHCID 11329766Methyl O-(3-bromophenyl)-N-triphenylmethyl-L-serinateHCID 162111393-Aminophenylboronic Acid Hemisulfate

Product 1

HCID 11353040Methyl O-(3'-amino-1,1'-biphenyl-3-yl)-N-triphenylmethyl-L-serinate

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 1140TolueneSolventHCID 80711,2-DimethoxyethaneSolvent

Procedure

Triphenyl arsine (0.31 g, 1.0 mmol, 0.1 equiv) and dichloro-bis(triphenylphosphine)-palladium(II) (0.35 g, 0.50 mmol, 0.05 equiv) were stirred under an argon atmosphere in DME (dimethoxy ethane; 56 mL) at rt for 30 min. Methyl O-(3-bromophenyl)-N-triphenylmethyl-L-serinate (Example 1) (5.16 g, 10.0 mmol, 1.0 equiv) and 3-amino phenyl boronic acid hemisulfate (2.2 g, 6.0 mmol, 1.2 equiv) were added as solids, followed by a 2M aqueous solution of cesium carbonate (15.0 mL, 30.0 mmol, 3 equiv). The reaction mixture was stirred for 3 h at rt and partioned between toluene and water. The organic layer was separated and dried over sodium sulfate. After filtration and evaporation of the solvents in vacuuo the crude product was purified by chromatography on SiO2 (gradient: toluene to toluene/-ethanol 97:3) Yield: 7.3 g, 39.0%. 1H NMR (CDCl3, 200 MHz) δ 7.65-7.40 (m, 10H); 7.25-7.12 (m, 11H); 6.97 (d, 2H); 4.70 (dd, 1H); 4.7 (dd, 1H); 3.75-3.65 (m, 3H); 3.24 (s, 3H); 2.90 (d, 1H). MS (DCI/NH3) 546 (M+NH4+), 529 (M+H); 234 (CPh3).

Workup

  1. customThe organic layer was separated
  2. dry with materialdried over sodium sulfate
  3. filtrationAfter filtration and evaporation of the solvents in vacuuo the crude product
  4. customwas purified by chromatography on SiO2 (gradient: toluene to toluene/-ethanol 97:3) Yield: 7.3 g, 39.0%

Sources & evidence

ORD record
ord-cce0981db5b44fe0bf6c13efc2754a9f
Source dataset
uspto-grants-2003_04
Patent number
US06545029B2

Reaction notes

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