o-Xylyl bromide → HCID 54269290, compound

HRID 1901076Notes

Reaction equation

[CH2:1]([O:8][C:9](=[O:23])[CH:10]1[CH2:15][CH2:14][N:13]([C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])[CH2:12][CH2:11]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C[Si]([N-][Si](C)(C)C)(C)C.[Na+].Br[CH2:35][C:36]1[C:37]([CH3:42])=[CH:38][CH:39]=[CH:40][CH:41]=1>C1COCC1>[CH2:1]([O:8][C:9](=[O:23])[C:10]1([CH2:35][C:36]2[CH:41]=[CH:40][CH:39]=[CH:38][C:37]=2[CH3:42])[CH2:11][CH2:12][N:13]([C:16]([O:18][C:19]([CH3:20])([CH3:22])[CH3:21])=[O:17])[CH2:14][CH2:15]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

Conditions

Temperature: -78 °C

Procedure

To a cold (-78° C.) solution of N-t-butoxycarbonyl isonipecotic acid benzyl ester (13.34 g, 41.8 mmol) in 140 ml of dry THF was added a 1.0 M THF solution of sodium bis trimethysilylamide (59 ml, 59 mmol) over 15 min. The resulting orange solution was stirred at -78° C. for 1 h and then treated dropwise with α-bromo-o-xylene (6.8 ml, 50.7 mmol) and then allowed to warm slowly to room temp. overnight. The reaction was quenched with saturated aqueous NH4Cl, diluted with H2O, and extracted with EtOAc (2×). The combined organic extracts were washed with brine (2×), and concentrated in vacuo to an orange gum. Flash chromatography on silica with 20% to 30% EtOAc/hexane as eluent, combining appropriate fractions, and concentrating in vacuo, afforded the product as a white solid.

Workup

temperatureto warm slowly to room temp. overnight
customThe reaction was quenched with saturated aqueous NH4Cl
additiondiluted with H2O
extractionextracted with EtOAc (2×)
washThe combined organic extracts were washed with brine (2×)
concentrationconcentrated in vacuo to an orange gum
concentrationconcentrating in vacuo

Sources & evidence

ORD record: ord-73fe703b86404613b9048af86ee66577
Source dataset: uspto-grants-1996_11
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05576313

Reaction notes

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