Selective α-amination and α-acylation of esters and amides via dual reactivity of O-acylhydroxylamines toward zinc enolates.
نویسندگان
چکیده
Selective α-amination and α-acylation of esters and amides have been developed, employing O-acylhydroxylamines as a dually reactive aminating and acylating reagent. Treatment of zinc enolates with O-acylhydroxylamines provides solely 1,3-dicarbonyl compounds under mild conditions. Introduction of a copper catalyst into the system shifts the reactivity entirely, yielding α-amination products exclusively.
منابع مشابه
Chemo- and Stereoselective Transition-Metal-Free Amination of Amides with Azides
The synthesis of α-amino carbonyl/carboxyl compounds is a contemporary challenge in organic synthesis. Herein, we present a stereoselective α-amination of amides employing simple azides that proceeds under mild conditions with release of nitrogen gas. The amide is used as the limiting reagent, and through simple variation of the azide pattern, various differently substituted aminated products c...
متن کاملSynthesis of α-diazo-β-keto esters, phosphonates and sulfones via acylbenzotriazole-mediated acylation of a diazomethyl anion.
We report a method for the synthesis of α-diazo-β-keto esters, phosphonates and sulfones via acylation of corresponding diazomethyl anions with N-acylbenzotriazoles. The N-o-amino-acylbenzotriazoles exhibited an unprecedented transphosphorylation reaction leading to diazoacetyl phenylphosphoramidates.
متن کاملTandem one-pot synthesis of polysubstituted NH-pyrroles involving the palladium-catalyzed intramolecular oxidative amination of the zinc bromide complex of β-enamino esters.
The Pd-catalyzed oxidative olefin amination of the zinc bromide complex intermediate, formed by the sequential reaction of nitriles with a Reformatsky reagent and 1-alkynes, affords pyrrole derivatives in good to excellent yields. This tandem protocol provides a simple, efficient, and atom- and pot-economical way to quickly build polysubstituted NH-pyrroles starting from readily available reage...
متن کاملChemistry of the Alkaline Earth Metal Enolates
Aldehydes, ketones, carboxylic esters, carboxylic amides, imines and N,N-disubstituted hydrazones react as electrophiles at their sp2-hybridized carbon atoms. These compounds also become nucleophiles, if they contain an H atom in the a-position relative to their C O or C N bonds. This is because they can undergo tautomerization to the corresponding enol as seen in Chapter 12. They are also C,H-...
متن کاملNi-Catalyzed α-arylation of esters and amides with phenol derivatives.
A nickel-catalyzed α-arylation of esters and amides with phenol derivatives has been accomplished. In the presence of our unique nickel catalyst, prepared in situ from Ni(cod)2, 3,4-bis(dicyclohexylphosphino)thiophene (dcypt), and K3PO4, various esters and amides undergo α-arylation with O-arylpivalates or O-arylcarbamates to afford the corresponding coupling products. The thus obtained α-aryl ...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید
ثبت ناماگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید
ورودعنوان ژورنال:
- Chemical communications
دوره 50 19 شماره
صفحات -
تاریخ انتشار 2014