Cesium carbonate → 2-Dimethylamino-6-vinyl-isonicotinic acid tert-butyl ester

HRID 1908753Notes

Reaction equation

[C:1]([O:5][C:6](=[O:17])[C:7]1[CH:12]=[C:11]([N:13]([CH3:15])[CH3:14])[N:10]=[C:9](Cl)[CH:8]=1)([CH3:4])([CH3:3])[CH3:2].C([O-])([O-])=O.[Cs+].[Cs+].B1(C=C)OB([CH:30]=[CH2:31])OB(C=C)O1.C1C=CN=CC=1>O1CCOCC1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[C:1]([O:5][C:6](=[O:17])[C:7]1[CH:8]=[C:9]([CH:30]=[CH2:31])[N:10]=[C:11]([N:13]([CH3:15])[CH3:14])[CH:12]=1)([CH3:4])([CH3:3])[CH3:2]

Participants

Conditions

Temperature: 100 °C

Procedure

To a solution of 2-chloro-6-dimethylamino-isonicotinic acid tert-butyl ester (770 mg, 3.00 mmol) in dioxane (45 mL), Cs2CO3 (1270 mg, 3.90 mmol) followed by P(tert.-Bu)3 (30 mg, 0.15 mmol) and 2,4,6-trivinylcyclotriboroxane pyridine complex (722 mg, 3.00 mmol, prepared according to F. Kerins, D. F. O'Shea J. Org. Chem. 67 (2002) 4968-4971) is added. The mixture is degassed and put under argon before Pd2(dba)3 (82 mg, 0.09 mmol) is added. The mixture is stirred at 100° C. for 15 h before it is cooled to rt and filtered over a short silica gel pad eluting with DCM. The filtrate is concentrated and purified on prep. TLC plates with DCM to give 2-dimethylamino-6-vinyl-isonicotinic acid tert-butyl ester (885 mg) as a red to brownish resin; LC-MS: tR=0.82 min, [M+1]+=249.37.

Workup

customThe mixture is degassed
additionis added
temperatureis cooled to rt
filtrationfiltered over a short silica gel pad
washeluting with DCM
concentrationThe filtrate is concentrated
custompurified on prep

Sources & evidence

ORD record: ord-55ab860aa8ae49b9bde8af746e6dca62
Source dataset: uspto-grants-2013_12
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08598208B2

Reaction notes

Loading…