Tetramethyltin → HCID 58604067, compound

HRID 2113664Notes

Reaction equation

HRID 2113664 reaction equation
Br[C:2]1[C:3](=[O:24])[CH2:4][C:5]2([CH2:20][CH2:21][CH2:22][CH3:23])[CH2:14][CH2:13][C:12]3[C:7](=[CH:8][CH:9]=[C:10]([O:16][CH2:17][O:18][CH3:19])[C:11]=3[Br:15])[C:6]=12.[CH3:25][Sn](C)(C)C.[Cl-].[Li+].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>CN(C)C=O.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[Br:15][C:11]1[C:10]([O:16][CH2:17][O:18][CH3:19])=[CH:9][CH:8]=[C:7]2[C:12]=1[CH2:13][CH2:14][C:5]1([CH2:20][CH2:21][CH2:22][CH3:23])[CH2:4][C:3](=[O:24])[C:2]([CH3:25])=[C:6]12

Participants

7

Reactant 4

HCID 11661TetramethyltinHCID 11776TriphenylphosphineHCID 433294Lithium ChlorideHCID 58604072HCID 58604072, compound

Product 1

HCID 58604067HCID 58604067, compound

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of 1,6-dibromo-3a-butyl-7-(methoxymethoxy)-3,3a,4,5-tetrahydro-2H-cyclopenta[a]naphthalen-2-one (71 mg, 0.15 mmol), dichlorobis(triphenylphosphine)palladium(II) (16 mg, 0.022 mmol), tetramethyltin (0.053 mL, 0.36 mmol), lithium chloride (13 mg, 0.30 mmol), and triphenylphosphine (8 mg, 0.03 mmol) in anhydrous N,N-dimethylformamide (DMF, 0.75 mL) was placed under a N2 atmosphere and heated in an oil bath at 100° C. for 2 days. After cooling, the mixture was concentrated under vacuum, the residue was taken up in CHCl3 and filtered through a pad of silica gel, and the filtrate was evaporated under vacuum to provide an oil. This material was purified by preparative layer chromatography on a 0.1×20×20 cm silica gel GF plate (Analtech, Newark, Del.), developing with 2:1 hexane-EtOAc. The UV visible band at Rf 0.44-0.50 was eluted with EtOAc and the eluant evaporated under vacuum to provide 6-bromo-3a-butyl-7-(methoxymethoxy)-1-methyl-3,3a,4,5-tetrahydro-2H-cyclopenta[a]naphthalen-2-one contaminated with approximately 10% of 3a-butyl-7-(methoxymethoxy)-1,6-dimethyl-3,3a,4,5-tetrahydro-2H-cyclopenta[a]naphthalen-2-one.

Workup

  1. temperatureAfter cooling
  2. concentrationthe mixture was concentrated under vacuum
  3. filtrationfiltered through a pad of silica gel
  4. customthe filtrate was evaporated under vacuum
  5. customto provide an oil
  6. customThis material was purified by preparative layer chromatography on a 0.1×20×20 cm silica gel GF plate (Analtech, Newark, Del.)
  7. washThe UV visible band at Rf 0.44-0.50 was eluted with EtOAc
  8. customthe eluant evaporated under vacuum

Sources & evidence

ORD record
ord-0b5cb1fb0a3d4eb0b2f3b4ab2c156e31
Source dataset
uspto-grants-2008_10
Patent number
US07432284B2

Reaction notes

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