Dichloromethane → HCID 118036474, compound

HRID 1778018Notes

Reaction equation

HRID 1778018 reaction equation
Cl[C:2]1[CH:3]=[CH:4][C:5]2[CH2:11][CH2:10][CH2:9][CH2:8][N:7]([C:12]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13])[C:6]=2[N:19]=1.[B-](F)(F)(F)[CH:21]=[CH2:22].[K+].C(Cl)Cl.C([O-])([O-])=O.[Cs+].[Cs+]>C1COCC1.O.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH:21]([C:2]1[CH:3]=[CH:4][C:5]2[CH2:11][CH2:10][CH2:9][CH2:8][N:7]([C:12]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13])[C:6]=2[N:19]=1)=[CH2:22]

Participants

8

Reactant 4

HCID 6344DichloromethaneHCID 10796Cesium carbonateHCID 10379064tert-Butyl 2-chloro-7,8-dihydro-5H-pyrido[2,3-b]azepine-9(6H)-carboxylateHCID 23679353Potassium vinyltrifluoroborate

Product 1

HCID 118036474HCID 118036474, compound

Reagents, catalysts & solvents 3

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 962WaterSolvent2×HCID 8028TetrahydrofuranSolvent

Procedure

A degassed mixture of tert-butyl 2-chloro-7,8-dihydro-5H-pyrido[2,3-b]azepine-9(6H)-carboxylate (690 mg, 2.44 mmol), potassium trifluoro(vinyl)borate (344 mg, 2.44 mmol), PdCl2(dppf). CH2Cl2 (199 mg, 0.244 mmol) and Cs2CO3 (2.00 g, 6.1 mmol) in THF (50 ml) and H2O (10 ml) was heated at 80° C. for 3.5 h. The reaction mixture was diluted with H2O and extracted with DCM (2×). The combined organic layers were dried over Na2SO4 and evaporated. The crude material was applied to a 120 g RediSep® silica column and purified by normal phase chromatography, eluting with 1:3 EtOAc/heptanes. Product-containing fractions were combined and evaporated to give the title compound as an off-white solid. (UPLC-MS 6) tR 1.18; ESI-MS 275.2 [M+H]+.

Workup

  1. extractionextracted with DCM (2×)
  2. dry with materialThe combined organic layers were dried over Na2SO4
  3. customevaporated
  4. custompurified by normal phase chromatography
  5. washeluting with 1:3 EtOAc/heptanes
  6. customevaporated

Sources & evidence

ORD record
ord-c9cc8e62fc5a4ba4af5dea2498362bf4
Source dataset
uspto-grants-2016_02
Patent number
US09266883B2

Reaction notes

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