Julia-Type Methylenation Reagent Usable for Ketones and Aldehydes under Mild Conditions

・Effective for the Methylenation of Various Ketones and Aldehydes
・High Reactivity at Room Temperature
・Easy to Remove Byproducts by Extraction

To a solution of M2860 (0.076 g, 0.36 mmol) and p-methoxyacetophenone (0.045 g, 0.30 mmol) in DMF (1.5 mL) under argon is added tert-BuOK (0.101 g, 0.90 mmol) at room temperature. After stirring for 1 h, the reaction is quenched with an aqueous NH₄Cl solution and the mixture is extracted with AcOEt (2 x 10 mL). The combined extracts are washed with H₂O (3 x 10 mL), brine, dried (MgSO₄), and concentrated. Column chromatography (silica gel; hexane : AcOEt = 10 : 1) provides 2-(4-methoxyphenyl)propene (0.041 g, 92%) as a colorless solid.

content of the research
Ando’s Laboratory has been working on the development of methodology of stereoselective synthesis of alkenes. By developing (ArO)₂P(O)CH₂CO₂Et, her group made it possible to synthesize cis-α,β-unsaturated esters selectively, which were hard to obtain by conventional methods. (These reagents are available at TCI). Her method can be applied to the synthesis of cis-α,β-unsaturated amides and nitriles as well. Since this method cannot be applied for stereoselective synthesis of alkenes, they are currently working on the development of a new methodology using the Peterson reaction and the Julia-Kocienski reaction.