Dichloromethane → Tert-butyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,2,3,6-tetrahydropyridine-1-carboxylate

HRID 1171022Notes

Reaction equation

HRID 1171022 reaction equation
FC(F)(F)S(O[C:7]1[CH2:8][CH2:9][N:10]([C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])[CH2:11][CH:12]=1)(=O)=O.[B:22].[B].[OH:24][C:25]([C:28]([OH:31])([CH3:30])[CH3:29])([CH3:27])[CH3:26].C([O-])(=O)C.[K+].ClCCl>CN(C)C=O>[CH3:26][C:25]1([CH3:27])[C:28]([CH3:30])([CH3:29])[O:31][B:22]([C:7]2[CH2:8][CH2:9][N:10]([C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])[CH2:11][CH:12]=2)[O:24]1

Participants

6

Reactant 4

HCID 6344DichloromethaneHCID 517044Potassium AcetateHCID 10991161Tert-butyl 4-(trifluoromethanesulfonyloxy)-1,2,3,6-tetrahydropyridine-1-carboxylateHCID 86590017Pinacol diboron

Product 1

HCID 4642098Tert-butyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,2,3,6-tetrahydropyridine-1-carboxylateYield 116.3%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
85 °C

Procedure

A mixture of tert-butyl 4{[(trifluoromethyl)sulfonyl]oxy}-1,2,3,6-tetrahydro-1-pyridinecarboxylate (1.8 g, 2.42 mmol), pinacol diboron (1.4 g, 5.44 mmol), potassium acetate (1.6 g, 16.32 mmol) and [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) complex with dichloromethane (0.27 g, 0.33 mmol) in N,N-dimethylformamide (30 mL) was heated in an 85° C. oil bath for 17 hours. The solvent was evaporated under reduced pressure then the residue was triturated with dichloromethane (30 mL). The mixture was filtered through a bed of diatomaceous earth then the solvents were evaporated under reduced pressure and the residue purified by flash chromatography on silica gel with heptane/ethyl acetate (8:2) as an eluent. The appropriate fractions were concentrated under reduced pressure to provide the title compound as a crystalline solid (0.87 g, 52%); TLC RF 0.44, heptane/ethyl acetate (8:2), visualized by PMA/heat, Silica Gel 60 F254 plates; 1H NMR (CDCl3, 400 MHz) δ 6.46 (m, 1H), 3.94 (m, 2H), 3.43 (m, 2H), 2.21 (m, 2H), 1.45 (s, 9H), 1.26 (s, 12H)

Workup

  1. customThe solvent was evaporated under reduced pressure
  2. customthe residue was triturated with dichloromethane (30 mL)
  3. filtrationThe mixture was filtered through a bed of diatomaceous earth
  4. customthe solvents were evaporated under reduced pressure
  5. customthe residue purified by flash chromatography on silica gel with heptane/ethyl acetate (8:2) as an eluent
  6. concentrationThe appropriate fractions were concentrated under reduced pressure

Sources & evidence

ORD record
ord-7acc0d5a1f8149a497af473a42bb3ecf
Source dataset
uspto-grants-2010_11
Patent number
US07829570B2

Reaction notes

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