Ethyl Acetate → US10023592, Example 315

HRID 518511Notes

Reaction equation

HRID 518511 reaction equation
[CH:1]1([CH2:4][CH2:5][C:6]2[CH:11]=[CH:10][C:9]([S:12]([CH3:15])(=[O:14])=[O:13])=[CH:8][C:7]=2I)[CH2:3][CH2:2]1.[CH3:17][N:18]1[CH:23]=[C:22](B2OC(C)(C)C(C)(C)O2)[CH:21]=[CH:20][C:19]1=[O:33].C([O-])([O-])=O.[Na+].[Na+].CC(=O)OCC>CN(C=O)C.O.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[CH:1]1([CH2:4][CH2:5][C:6]2[CH:11]=[CH:10][C:9]([S:12]([CH3:15])(=[O:14])=[O:13])=[CH:8][C:7]=2[C:22]2[CH:21]=[CH:20][C:19](=[O:33])[N:18]([CH3:17])[CH:23]=2)[CH2:3][CH2:2]1

Participants

7

Reactant 4

HCID 8857Ethyl Acetate2×HCID 10340Sodium CarbonateHCID 454801941-Methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridin-2(1H)-oneHCID 1180219661-(2-Cyclopropylethyl)-2-iodo-4-methylsulfonylbenzene

Product 1

HCID 118021519US10023592, Example 315Yield 55%

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 21962138N,N-Dimethylformamide--water (1/1)Solvent

Procedure

The title compound of step 3 (120 mg, 0.34 mmol), 1-methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridin-2-one (89 mg, 0.37 mmol), Na2CO3 (72 mg, 0.68 mmol) and Pd(dppf)Cl2 (15 mg) in DMF/H2O (6 ml/1.5 ml) under N2 were heated at 100° C. for 1 h. EA extractive work up and preparative TLC (PE: EtOAc=0:1) gave the title compound (62 mg, 55%). 1H NMR (CD3OD, 400 MHz): δ 7.92 (dd, J1=2.4 Hz, J2=5.6 Hz, 1H), 7.81 (d, J=2 Hz, 1H), 7.78 (d, J=2.4 Hz, 1H), 7.65-7.61 (m, 2H), 6.69 (m, J=9.2 Hz, 1H), 3.69 (s, 3H), 3.17 (s, 3H), 2.89-2.86 (m, 2H), 1.51-1.45 (m, 2H), 0.68-0.65 (m, 1H), 0.45-0.40 (m, 2H), 0.04-0.00 (m, 2H). LCMS: 332 (M+1)+

Sources & evidence

ORD record
ord-0c4ddee27fa943a68cddce5ad20d5c34
Source dataset
uspto-grants-2015_08
Patent number
US09115114B2

Reaction notes

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