Water → (2SR,4RS)-4-cyano-2-methyl-4-(3-triisopropylsilylthiophenyl)-3,4,5,6-tetrahydro-2H-pyran

HRID 1108103Notes

Reaction equation

HRID 1108103 reaction equation
[CH:1]([Si:4]([CH:9]([CH3:11])[CH3:10])([CH:6]([CH3:8])[CH3:7])[SH:5])([CH3:3])[CH3:2].[H-].[Na+].[C:14]([C:16]1([C:23]2[CH:28]=[CH:27][CH:26]=[C:25](I)[CH:24]=2)[CH2:21][CH2:20][O:19][CH:18]([CH3:22])[CH2:17]1)#[N:15].O>C1(C)C=CC=CC=1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[C:14]([C:16]1([C:23]2[CH:28]=[CH:27][CH:26]=[C:25]([S:5][Si:4]([CH:1]([CH3:3])[CH3:2])([CH:6]([CH3:8])[CH3:7])[CH:9]([CH3:11])[CH3:10])[CH:24]=2)[CH2:21][CH2:20][O:19][CH:18]([CH3:22])[CH2:17]1)#[N:15]

Participants

7

Reactant 4

HCID 962WaterHCID 24758Sodium hydrideHCID 3435097Tris(propan-2-yl)silanethiolHCID 18786332(2SR, 4RS)-4-cyano-4-(3-iodophenyl)-2-methyl-3,4,5,6-tetrahydro-2H-pyran

Product 1

HCID 18786333(2SR,4RS)-4-cyano-2-methyl-4-(3-triisopropylsilylthiophenyl)-3,4,5,6-tetrahydro-2H-pyranYield 96.5%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 1140TolueneSolvent2×

Conditions

Temperature
80 °C

Procedure

To a stirred solution of triisopropylsilanethiol (Tetrahedron Lett. 1994, 35, 3221.; 684 mg, 3.6 mmol) in toluene (5 ml) was added sodium hydride (60% oil dispersion, 144 mg, 3.6 mmol) under a nitrogen atmosphere. After stirring for 15 min, the resulting solution was added to a mixture of (2SR, 4RS)-4-cyano-4-(3-iodophenyl)-2-methyl-3,4,5,6-tetrahydro-2H-pyran (1.07 g, 3.27 mmol) and tetrakis(triphenylphosphine)palladium(0) (114 mg, 0.1 mmol) in toluene (20 ml), and the mixture was heated at 80° C. for 1 h. The resulting mixture was cooled, poured into water (50 ml) and extracted with Et2O (100 ml). The organic extract was washed with water (50 ml), brine (50 ml), dried (MgSO4) and concentrated. Purification by silica gel column chromatography, eluting with ethyl acetate-hexane (1:9), gave 1.23 g (96%) of the titled compound as a red oil.

Workup

  1. temperatureThe resulting mixture was cooled
  2. extractionextracted with Et2O (100 ml)
  3. extractionThe organic extract
  4. washwas washed with water (50 ml), brine (50 ml)
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated
  7. customPurification by silica gel column chromatography
  8. washeluting with ethyl acetate-hexane (1:9)

Sources & evidence

ORD record
ord-d17c85bec5ee44eb9ea841e5893ded23
Source dataset
uspto-grants-2000_05
Patent number
US06063928

Reaction notes

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