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International audience; We herein demonstrate the acylsilane-directed Rh-catalyzed arene C-H bond alkylation with maleimides. The resulting derivatives were utilized in visible-light-induced intramolecular siloxycarbene-amide cyclization for the synthesis of new tricyclic γ-lactams. In parallel, we also harnessed the same acylsilane and maleimide units through [3 + 2] carbo-annulation by using Ru-catalysis. A wide range of maleimides and aroylsilanes were used to establish the broadness of these transformations.

A rare dipolarophile-induced diastereo-selective amidative annulation and concomitant 3 + 2 cycloaddition are reported using α-amino acids, amino aldehydes and maleimides.

A formal diastereoselective 1,3-dipolar cycloaddition of azomethine ylide and coumarin derivatives to construct coumarin based spiro multi heterocyclics has been described. The in situ generation of azo-ylide was achieved for various heterocyclic carbonyls (indenoquinoxaline and isatin). This transformation is also suitable for maleimide dipolarophiles for the synthesis of hydro-maleimide derivatives. These decarboxylative annulations neither required any catalyst nor any activator. Further the pure products were isolated by filtration from the reaction mixture after the reaction under ambient conditions.

2-Aminoindole-3-carboxylates undergo a Lewis-acid-catalyzed decarboxylative annulation with ynals to afford dihydrochromeno-fused δ-carbolines through a 2,3-aza migration, via a spirocyclic intermediate generated from an initial [3 + 2] spirocycloaddition. Brønsted acid interference changes the path from a [3 + 2] to a [4 + 2] addition. 2-Aminoindoles without an ester functional group at C3 underwent a different condensation, followed by hetero-Diels-Alder reaction to generate chromeno-fused α-carbolines.

A regioselective carbonickelation followed by cyclization, an arylative cyclization, of ortho functional diaryl acetylenes is achieved apparently through an electrophile driven alkyne polarization. A series of selectively substituted di aryl isoquinoline, pyridine and indene derivatives are thus accessed from diarylacetylenes with azide, carbonyl and cyanide tethers.

A general method for highly functionalized 2-pyrones via a base-mediated sequential vinylogous addition and cyclization of γ-phosphonyl/sulfonyl crotonates and ynones are described. An exclusive E-geometry with respect to the newly generated olefin substituent at C3 of pyrone was observed. Imino glyoxalates and glycine imines similarly reacted with ynones to deliver 3-imino pyrones.

[4 + 2] oxidative Diels-Alder reaction of readily available alkynols with maleimide is achieved for the rapid access of pthalimide-fused multicyclic compounds. The reaction is proposed to go through a sequence of Sc(OTf)

A formal intramolecular vicinal 1,2-diamination of alkynes is achieved for the synthesis of indole-cyclic urea fused derivatives through a double cyclization process from readily available aminophenyl propargyl alcohols. This sequential triple C-N bond construction event was possible using isocyanate as urea precursor and Ag(I) catalyst as alkyne activating agent. Control experiments reveal that the cyclization, followed by 1,3-allylic amino dehydroxylation, is preceded by urea formation.

Access to furanyl- and pyrrolyl-3-carboxamides from readily available 3-alkyne-1,2-diols and 1-amino-3-alkyn-2-ols using isocyanate as amido surrogate is demonstrated. The approach constitutes a successful unprecedented combination of heteropalladation and isocyanate insertion, a new avenue for novel amide bond constructions. The mechanism likely involves a 6-membered oxaaminopalladacycle as the key intermediate.

A syn-arylative nickelation followed by nucleophilic syn-selective cyclization of o-propargyloxy benzaldehydes is achieved toward the synthesis of chromanol skeletons with alkenyl substitution at C3. The capture of the intermediate vinyl nickel in its cis geometry is done also with a Michael acceptor to synthesize 4-alkylated derivatives. This protocol is equally applicable to o-propargylamino benzaldehydes to access 3,4-disubstituted tetrahydro-hydroquinolines.

An anti-carbonickelative cyclization via reversible alkenylnickel E/Z isomerization of 2-azido phenyl propargyl alcohols with aryl boronic acids is achieved using Ni(acac)2 as the catalyst to access 2,3-diaryl quinolines. It represents a rare example of trapping the vinyl metal intermediate with a nitrogen center, a non-carbon center electrophile.

A regio- and stereoselective thiocyanate addition to ynones is achieved using KSCN in AcOH at 70 °C. The reaction is extendable to ynals, ynesulfones, ynoic acids and ynoates. Adducts from ynones were readily transformed into thiazine-2-thione derivatives under slightly modified reaction conditions. In contrast, thiocyanated adducts from ynamides underwent an in situ decyanative amido cyclization towards isothiazolones. None of these events needed any transition metal or catalyst, attaining a high synthetic value.

An unusual Pd-catalyzed isocyanide assisted 5-exo-dig reductive cyclization of 1-(2-hydroxyphenyl)-propargyl alcohols is achieved for 2-alkyl/benzyl benzofurans. The reaction features a high substrate scope, insensitivity to air, and excellent product yielding. Further, a direct metal-free C–H functionalization (azidation, alkoxylation, and hydroxylation) and selective oxidative cleavage of thus synthesized 2-benzylfurans are described for azido-, alkoxy-, hydroxyl-, amide-, and tetrazolyl adducts.

An unusual Pd-catalyzed isocyanide assisted 5-exo-dig reductive cyclization of 1-(2-hydroxyphenyl)-propargyl alcohols is achieved for 2-alkyl/benzyl benzofurans. The reaction features a high substrate scope, insensitivity to air, and excellent product yielding. Further, a direct metal-free C–H functionalization (azidation, alkoxylation, and hydroxylation) and selective oxidative cleavage of thus synthesized 2-benzylfurans are described for azido-, alkoxy-, hydroxyl-, amide-, and tetrazolyl adducts.