Direct Access to Isoindolin‐1‐one Scaffolds by Copper‐Catalyzed Divergent Cyclizations of 2‐Formylbenzonitrile and Diaryliodonium Salts

Abstract

Copper‐catalyzed cascade transformations of 2‐formylbenzonitrile and diaryliodonium salts were carried out to efficiently afford isoindolin‐1‐one scaffolds. The process proceeds through a copper‐catalyzed tandem C–H/N–H arylation, producing two different isoindolin‐1‐one derivatives under different reaction conditions.magnified image

Isoindolinone Synthesis via One‐Pot Type Transition Metal Catalyzed C−C Bond Forming Reactions

“…By selecting suitable catalyst and hypervalent iodine reagent, a divergent cyclization was initially developed forming either 2,3‐diarylisoindolinone derivatives or polycyclic compounds containing two isoindolinone scaffolds in moderate to good yields (Scheme 97 A). [184a] The methodology for 2,3‐diaryl substituted isoindolinone synthesis was further extended to a multicomponent reaction allowing for more flexible synthesis of various isoindolinone derivatives (Scheme 97 B). [184b] Unsymmetrical diaryliodonium salts could be replaced by combination of symmetric diaryliodonium salts with a suitable arene.…”

Atom-economical group-transfer reactions with hypervalent iodine compounds

“…However, the high steric demand can be of disadvantage if the development of an atom-economical transformation is intended through a subsequent functionalization of the emerging, now less reactive, mesityl iodide. A procedure which impressively combines the selectivity of mesityl(aryl)iodonium salts 1a with this difficult second arylation step was developed by Li and co-workers [ 31 ]. Under copper-catalysis diarylated isoindolin-1-ones 9 were formed starting from 2-formylbenzonitriles 8 upon treatment with mesityl(aryl)iodonium salts 1a ( Scheme 6 ).…”

Synthesis and Organocatalytic Asymmetric Nitro-aldol Initiated Cascade Reactions of 2-Acylbenzonitriles Leading to 3,3-Disubstituted Isoindolinones

“…A feature of this sequence of reactions relies on the selectivity of the Wittig reaction of the readily available 2-cyanobenzaldehyde 5 (Scheme 1), in which the cyano group in the 2 position is left non-reacted, while 2-cyanobenzaldehyde is reported to give efficient cascade reactions involving both the aldehyde and the cyano group. This leads to valuable 3-monosubstituted isoindolinones in the presence of a number of carbonand hetero-nucleophiles [21][22][23][24][25][26][27][28][29][30]. The cis/trans olefin mixture 6 was, then, hydrogenated under heterogeneous conditions and, taking advantage from our previous work [8], the obtained 2-alkylbenzonitriles 4 were selectively oxidized at the benzylic position with NBS/AIBN/H 2 O to afford the desired ketones 3 in good yields (Scheme 1).…”