Pyridine → HCID 57941372, compound

HRID 1437967Notes

Reaction equation

HRID 1437967 reaction equation
[C:1]1([N:7]2[C:15]3[C@@:14]4([CH3:19])[C:16]([CH3:18])([CH3:17])[C@H:11]([CH2:12][CH2:13]4)[C:10]=3[C:9](=[O:20])[NH:8]2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[C:21]1(B(O)O)[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1.N1C=CC=CC=1>ClCCl.O.C([O-])(=O)C.[Cu+2].C([O-])(=O)C>[CH3:19][C@@:14]12[C:16]([CH3:17])([CH3:18])[C@@H:11]([C:10]3[C:9](=[O:20])[N:8]([C:21]4[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=4)[N:7]([C:1]4[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=4)[C:15]=31)[CH2:12][CH2:13]2

Participants

7

Reactant 3

HCID 1049PyridineHCID 66827Phenylboronic AcidHCID 57250492HCID 57250492, compound2×

Product 1

HCID 57941372HCID 57941372, compoundYield 44.7%

Reagents, catalysts & solvents 3

HCID 8895Cupric acetateCatalystHCID 962WaterSolventHCID 6344DichloromethaneSolvent2×

Procedure

A mixture of (4S,7R)-1-phenyl-7,8,8-trimethyl-1,2,4,5,6,7-hexahydro-4,7-methano-indazol-3-one (Intermediate 8; 1.00 g, 3.7 mmol), phenyl-boronic acid (0.94 g, 7.5 mmol), and copper(II) acetate (1.03 g, 5.6 mmol) in dichloromethane (10 mL) and pyridine (0.6 mL, 7.5 mmol) was stirred at room temperature for 2 days and then heated at reflux for 2 h. The reaction mixture was diluted with water and dichloromethane. The aqueous layer was extracted twice with dichloromethane, and the combined organic layers were washed with water, 10% copper(II) sulfate solution, water, and brine. The solution was then dried (magnesium sulfate), filtered, evaporated and purified using an Analogix Intelliflash 280 system (Analogix, Inc., Burlington, Wis.) with an Analytical Sales Aspire 90 g column, eluting with 10-50% ethyl acetate/hexanes to give (4S,7R)-7,8,8-trimethyl-1,2-diphenyl-1,2,4,5,6,7-hexahydro-4,7-methano-indazol-3-one (0.57 g, 44%) as a light brown solid. ES(+)-MS (M+H) 345.

Workup

  1. temperatureheated
  2. temperatureat reflux for 2 h
  3. extractionThe aqueous layer was extracted twice with dichloromethane
  4. washthe combined organic layers were washed with water, 10% copper(II) sulfate solution, water, and brine
  5. dry with materialThe solution was then dried (magnesium sulfate)
  6. filtrationfiltered
  7. customevaporated
  8. custompurified
  9. washeluting with 10-50% ethyl acetate/hexanes

Sources & evidence

ORD record
ord-7323e83a756f43139df47fec919181f1
Source dataset
uspto-grants-2009_11
Patent number
US07622492B2

Reaction notes

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