1-Bromo-4-iodobenzene → 8-(4-Bromophenyl)-1,4-dioxa-8-azaspiro[4.5]decane

HRID 715558Notes

Reaction equation

[O:1]1[C:5]2([CH2:10][CH2:9][NH:8][CH2:7][CH2:6]2)[O:4][CH2:3][CH2:2]1.[Br:11][C:12]1[CH:17]=[CH:16][C:15](I)=[CH:14][CH:13]=1.CC(C)([O-])C.[Na+]>C1(C)C=CC=CC=1>[Br:11][C:12]1[CH:17]=[CH:16][C:15]([N:8]2[CH2:9][CH2:10][C:5]3([O:4][CH2:3][CH2:2][O:1]3)[CH2:6][CH2:7]2)=[CH:14][CH:13]=1

Participants

Conditions

Temperature: 140 °C

Procedure

1,4-Dioxa-8-azaspiro[4.5]decane (1.63 mL) and 1-bromo-4-iodobenzene (3 g) are dissolved in toluene (75 mL), treated with sodium tert-butoxide (1.53 g) and purged for 10 minutes with argon. Acetato-(2′-di-tert.-butylphosphino-1,1′-biphenyl-2-yl)-palladium-(II) (245 mg) is added and the mixture is heated for 15 minutes at 140° C. Then the mixture is partitioned between saturated aqueous NH4Cl solution and ethylacetate. The organic phase is washed with brine and dried (MgSO4). The solvents are evaporated in vacuo and the residue is chromatographed on silica gel (cyclohexane/ethyl acetate 99:1→70:30) to give the title compound. LC (method 2): tR=1.06 min; Mass spectrum (ESI+): m/z=298 [M+H]+.

Workup

custompurged for 10 minutes with argon
additionAcetato-(2′-di-tert.-butylphosphino-1,1′-biphenyl-2-yl)-palladium-(II) (245 mg) is added
customThen the mixture is partitioned between saturated aqueous NH4Cl solution and ethylacetate
washThe organic phase is washed with brine
dry with materialdried (MgSO4)
customThe solvents are evaporated in vacuo
customthe residue is chromatographed on silica gel (cyclohexane/ethyl acetate 99:1→70:30)

Sources & evidence

ORD record: ord-137bf614439246dd856dd0edc3637b8b
Source dataset: uspto-grants-2015_11
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09187477B2

Reaction notes

Loading…