Metal-free oxidative tandem coupling of activated alkenes with carbonyl C(sp2)–H bonds and aryl C(sp2)–H bonds using TBHP

Abstract

A metal-free oxidative tandem coupling of activated alkenes with carbonyl C(sp 2 )-H bonds and aryl C(sp 2 )-H bonds using TBHP is established for the synthesis of 3-(2-oxoethyl)indolin-2-ones. This method allows 1,2-difunctionalization of the C-C double bond in N-arylacrylamides by simultaneous formation of two C(sp 2 )-C(sp 3 ) bonds. Scheme 1 Oxidative tandem coupling reaction. Scheme 2 Utilization of 3-(2-oxoethyl)indolin-2-ones.

Metal‐Free Aryltrifluoromethylation of Activated Alkenes

“…A substrate with a para-chlorobenzoate substituent on the nitrogen atom was converted into 3 d, the structure of which was confirmed by X-Ray diffraction analysis. [13] When a trisubstituted alkene (R 5 = Me) was used, the cyclized aryltrifluoromethylation product 3 e was obtained in 59 % yield as a 8:1 mixture of diastereoisomers, thus showing that good levels of stereocontrol could be attained in these transformations (Scheme 2).…”

“…We decided to further explore the regioselectivity of this benzannulation. [14] Various substrates bearing nonsymmetric arenes were synthesized. Interestingly, in the presence of electron-withdrawing groups at the R 1 position, the para cyclization products 3 f-h were selectively obtained.…”

Oxidative 1,2-carboamination of alkenes with alkyl nitriles and amines toward γ-amino alkyl nitriles

“…The decomposition the AgCH 2 CN intermediate B readily takes place under heating to form the alkyl radical C (supported by the results of Fig. 2b), AgHCO 3 and the Ag 0 species [Ag(s)] through single electron transfer424344454647484950515253545556575859606162636465. Subsequently, addition of the alkyl radical C across the C–C double bond in alkene 1a produces the alkyl radical intermediate D (supported by the reaction of alkene 1t ; Fig.…”

ChemInform Abstract: Microwave‐Assisted Copper‐Catalyzed Oxidative Cyclization of Acrylamides with Non‐Activated Ketones.

“…Increasing or decreasing the amount of acetophenone led to ar educed product yield (entries 8a nd 9). Also, any change in reactiont emperature led to an egative outcome (entries [10][11][12]. Interestingly,t he use of Et 3 N( 10 mol %) as an additive increased the yield to 78 %( entry 13).…”