Tetrahydrofuran → 8-Cyclopropyl-3,4-dihydro-4,4-dimethyl-6-(trimethylsilanyl)ethynylspiro[2 H 1-benzopyran-2,1'-cyclopropane]

HRID 395072Notes

Reaction equation

HRID 395072 reaction equation
Br[C:2]1[CH:3]=[C:4]([CH:16]2[CH2:18][CH2:17]2)[C:5]2[O:12][C:9]3([CH2:11][CH2:10]3)[CH2:8][C:7]([CH3:14])([CH3:13])[C:6]=2[CH:15]=1.[CH3:19][Si:20]([C:23]#[CH:24])([CH3:22])[CH3:21].C(N(CC)CC)C.O1CCCC1>CCCCCC.[Cu]I.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.C(OCC)(=O)C>[CH:16]1([C:4]2[C:5]3[O:12][C:9]4([CH2:11][CH2:10]4)[CH2:8][C:7]([CH3:13])([CH3:14])[C:6]=3[CH:15]=[C:2]([C:24]#[C:23][Si:20]([CH3:22])([CH3:21])[CH3:19])[CH:3]=2)[CH2:17][CH2:18]1

Participants

9

Reactant 4

HCID 8028TetrahydrofuranHCID 8471TriethylamineHCID 66111TrimethylsilylacetyleneHCID 225689116-Bromo-8-cyclopropyl-3,4-dihydro-4,4-dimethylspiro[2H-1-benzopyran-2,1'-cyclopropane]2×

Product 1

HCID 225688398-Cyclopropyl-3,4-dihydro-4,4-dimethyl-6-(trimethylsilanyl)ethynylspiro[2 H 1-benzopyran-2,1'-cyclopropane]

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8058HexaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

Following general procedure D and 6-bromo-8-cyclopropyl-3,4-dihydro-4,4-dimethylspiro[2H-1-benzopyran-2,1′-cyclopropane] (Intermediate 42, 0.74 g, 2.4 mmol), (trimethylsilyl)acetylene (4 mL, 28 mmol), triethyl amine (8 mL), anhydrous tetrahydrofuran, copper(I)iodide (0.050 g, 0.26 mmol) and dichlorobis(triphenylphosphine)palladium(II) (0.15 g, 0.22 mmol), followed by flash column chromatography over silica gel (230-400 mesh) using 1-2% ethyl acetate in hexane as the eluent, the title compound was obtained as an oil (0.62 g, 80%).

Sources & evidence

ORD record
ord-7dbb2b466fdd4527a67217c8aaad288d
Source dataset
uspto-grants-2003_08
Patent number
US06603019B2

Reaction notes

Loading…