2,4-Dichloropyridine → Ethyl 2-[(4-chloro-2-pyridinyl)amino]-1,3-oxazole-5-carboxylate

HRID 352

反応式

HRID 352 の反応式
CCOC(=O)c1cnc(N)o1.Clc1ccnc(Cl)c1>C1COCCO1.COc1ccc(OC)c(P(C(C)(C)C)C(C)(C)C)c1-c1c(C(C)C)cc(C(C)C)cc1C(C)C.O=C(/C=C/c1ccccc1)/C=C/c1ccccc1.O=C(/C=C/c1ccccc1)/C=C/c1ccccc1.O=C(/C=C/c1ccccc1)/C=C/c1ccccc1.O=C([O-])[O-].[Cs+].[Cs+].[Pd].[Pd]>CCOC(=O)c1cnc(Nc2cc(Cl)ccn2)o1

参加物

7

反応条件

温度
160 °C

実験手順

Objective: Series of experiments to optimise yield of the above coupled product. Pd2(dba)3 (22.89 mg, 0.025 mmol), di-tert- butyl(2',4',6'-triisopropyl-3,6-dimethoxybiphenyl-2-yl)phosphine (48.4 mg, 0.10 mmol), 2,4-dichloropyridine (148 mg, 1.00 mmol), cesium carbonate (651 mg, 2.00 mmol),ethyl 2-aminooxazole-5-carboxylate (156 mg, 1.00 mmol) and 4,4'-di-tert-butylbiphenyl (60 mg, 0.23 mmol) were added to an oven dried microwave vial, the vial was capped and placed under an inert atmosphere, dioxane (4 mL) was added and the resulting mixture was heated at 160 °C for 1 h by microwave irradiation under a nitrogen atmosphere. Crude LCMS shows a switch in regioselectivity, with the other isomer becoming the major product in 25% yield based on internal standard (note: this is a rough estimate as the U.V absorbance may be significantly different to the other regioisomer). The regioisomeric ratio is 1.7:1 and although the product was not formed in synthetically useful yields, it is an interesting result. Conclusion: Switch in regioselectivty with the change in ligand may be worth pursuing, although greater selectivity was seen for this prduct in the preceeding reaction.

出典と根拠

ORDレコード
ord-81c9dfb0f9224007985242064ea9e33c
出典データセット
750 AstraZeneca ELN dataset
元リンク
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