2-Bromopyridine → HCID 67336561, compound

HRID 1670541Notes

Reaction equation

HRID 1670541 reaction equation
C1C=CC(P(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CC(C)([O-])C.[Na+].Br[C:37]1[CH:42]=[CH:41][CH:40]=[CH:39][N:38]=1.[NH2:43][CH2:44][C:45]1[C:55]2[CH2:54][CH2:53][N:52]([C:56]([O:58][C:59]([CH3:62])([CH3:61])[CH3:60])=[O:57])[CH2:51][CH2:50][C:49]=2[CH:48]=[CH:47][C:46]=1[Cl:63]>C1(C)C=CC=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[C:59]([O:58][C:56]([N:52]1[CH2:53][CH2:54][C:55]2[C:45]([CH2:44][NH:43][C:37]3[CH:42]=[CH:41][CH:40]=[CH:39][N:38]=3)=[C:46]([Cl:63])[CH:47]=[CH:48][C:49]=2[CH2:50][CH2:51]1)=[O:57])([CH3:62])([CH3:60])[CH3:61]

Participants

7

Reactant 4

HCID 79732-BromopyridineHCID 812191,3-Bis(diphenylphosphino)propaneHCID 23676156Sodium t-butoxideHCID 59822294HCID 59822294, compound

Product 1

HCID 67336561HCID 67336561, compoundYield 203.5%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Conditions

Temperature
95 °C

Procedure

Add tris(dibenzylideneacetone)dipalladium(0) (52 mg, 0.06 mmol), DPPP (47 mg, 0.11 mmol), sodium tert-butoxide (26 mg, 0.27 mmol) and 2-bromopyridine (23 μl, 0.23 mmol) to a solution of 6-aminomethyl-3-tert-butoxycarbonyl-7-chloro-2,3,4,5-tetrahydro-1H-benzo[d]azepine (60 mg, 0.19 mmol) in anhydrous toluene (3 mL). Degas the slurry under house vacuum, then flush with nitrogen. Stir the mixture at 95° C. for 20 h. Cool the mixture to room temperature, dilute with diethyl ether (20 mL) and filter through Celite®. Concentrate the filtrate in vacuo to obtain crude 3-tert-butoxycarbonyl-7-chloro-6-(pyridin-2-ylaminomethyl)-2,3,4,5-tetrahydro-1H-benzo[d]azepine (150 mg). Continue processing with the crude mixture. MS (ES+) m/z: 388.2 (M+H)+.

Workup

  1. customDegas the slurry under house vacuum
  2. customflush with nitrogen
  3. temperatureCool the mixture to room temperature
  4. additiondilute with diethyl ether (20 mL)
  5. filtrationfilter through Celite®
  6. concentrationConcentrate the filtrate in vacuo

Sources & evidence

ORD record
ord-96a00ed012b9404c87b0385fa12af644
Source dataset
uspto-grants-2011_08
Patent number
US07994163B2

Reaction notes

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