ABSTRACT
We disclose a Ni-catalyzed regioselective dialkylation reaction of alkenylarenes with α-halocarbonyls and alkylzinc reagents. The reaction produces γ-arylated alkanecarbonyl compounds with the generation of two new C(sp3 )-C(sp3 ) bonds at the vicinal carbons of alkenes. This reaction is effective for the use of primary, secondary and tertiary α-halocarboxylic esters, amides and ketones in conjunction with primary and secondary alkylzinc reagents as the sources of two C(sp3 ) carbons for the dialkylation of terminal and cyclic internal alkenes.
ABSTRACT
We report a Cu(II)-catalyzed cyclization/coupling of alkenyl aldimines with arylzinc reagents to create indole-3-diarylmethane derivatives (Sapkota et al. ChemRxiv 2022, DOI: 10.26434/chemrxiv-2022-d6qn). The current reaction provides a unified modular route from readily available starting materials to indole-3-diarylmethanes in which all three arene cores can be decorated with differential functional substitutions on demand. Since the cyclization/coupling of alkenyl aldimines is unknown to date, the current method widens the scope with regard to both the substrate and product diversity for this class of reaction.
ABSTRACT
We disclose a Ni-catalyzed vicinal alkylarylation of unactivated alkenes in γ,δ-alkenylketimines with aryl halides and alkylzinc reagents. The reaction produces γ-C(sp3)-branched δ-arylketones with the construction of two new C(sp3)-C(sp3) and C(sp3)-C(sp2) bonds. Electron-deficient alkenes play crucial dual roles as ligands to stabilize reaction intermediates and to increase catalytic rates for the formation of C(sp3)-C(sp3) bonds. This alkene alkylarylation reaction is also effective for secondary alkylzinc reagents and internal alkenes, and proceeds with a complete regio- and stereocontrol, affording products with up to three contiguous all-carbon all-cis secondary stereocenters.
ABSTRACT
We disclose a nickel-catalyzed reaction, which enabled us to difunctionalize unactivated γ,δ-alkenes in ketones with alkenyl triflates and arylboronic esters. The reaction was made feasible by the use of 5-chloro-8-hydroxyquinoline as a ligand along with NiBr2 â DME as a catalyst and LiOtBu as base. The reaction proceeded with a wide range of cyclic, acyclic, endocyclic and exocyclic alkenyl ketones, and electron-rich and electron-deficient arylboronate esters. The reaction also worked with both cyclic and acyclic alkenyl triflates. Control experiments indicate that carbonyl coordination is required for the reaction to proceed.
ABSTRACT
Nanographenes are a popular area of research due to their promising properties for electronics. Over the last twenty years there has been a significant increase in interest in the development of contorted nanographenes. While many top-down techniques are employed in the synthesis of these planar nanographenes, the use of alkynes in bottom-up syntheses allows for easy functionalization and the development of contorted nanographenes. The syntheses of contorted nanographenes with a focus on utilizing alkynes is reviewed here.
Subject(s)
Alkynes/chemistry , Graphite/chemistry , Nanostructures/chemistry , Cyclization , Graphite/chemical synthesis , Molecular ConformationABSTRACT
We disclose a transmetalation-initiated Ni(I)-catalyzed regioselective ß,δ-vinylarylation of γ,δ-alkenyl α-cyanocarboxylic esters with vinyl triflates and arylzinc reagents. This reaction proceeds via contraction of six-membered nickellacycles to five-membered nickellacycles to form carbon-carbon bonds at the nonclassical homovicinal sites, and it provides expeditious access to a wide range of complex aliphatic α-cyanoesters, α-cyanocarboxylic acids, dicarboxylic acids, dicarboxylic acid monoamides, monocarboxylic acids, nitriles, and spirolactones. Control, deuterium labeling, and crossover experiments indicate that (i) the nickellacycle contraction occurs by ß-H elimination, followed by hydronickellation on transiently formed alkenes, and (ii) the Ni species are stabilized as Ni-enolates.
