NICKEL CATALYZED REDUCTIVE DEAMINATIVE ARYLATION AT sp 3 CARBON CENTERS
0
Citation
0
Reference
20
Related Paper
Keywords:
Carbon fibers
Cite
A palladium-catalyzed arylation of benzoxazole has been developed. This protocol involves the tandem decarboxylation and oxidation of a carbon–carbon triple bond followed by decarbonylative arylation of the benzoxazole C–H bond.
Benzoxazole
Decarboxylation
Tandem
Triple bond
Decarbonylation
Carbon fibers
Cite
Citations (10)
Transition-metal-catalyzed decarboxylative coupling reactions have gained considerable attention over the past decade as an efficient route to form heterobiaryls. However, current methods for oxidative decarboxylative (hetero)arylation with unactivated C-H bonds have been limited by poor substrate scope, control of regioselectivity, and chemospecificity. This thesis describes the development of a new nickel-catalyzed oxidative decarboxylative coupling (ODC) with unactivated C-H bonds. The first chapter discusses the development of the new nickel-catalyzed ODC reaction to enable the coupling of a N,N'-bidentate directing group with a broad scope of heteroaromatic carboxylates and ortho-substituted benzoates, a scope that has not been achieved in previous oxidative decarboxylative coupling transformations. The following chapter is an extension of the nickel-catalyzed ODC reaction for the synthesis of heterocyclecontaining phenanthridinones. This chapter details an oxidative decarboxylative annulation with heteroaromatic carboxylates and ortho-fluorobenzoates. The final chapter describes the investigation and attempted synthesis of a proposed Ni(II) metallacycle from our catalytic cycles in the previous chapters. Synthesis of a Ni(II) metallacycle by denitrogenation of 3‐(quinolin‐8‐yl)‐3,4‐dihydro‐1,2,3‐benzotriazin‐4‐one led to an interesting azanickelacycle dimer. However, decarbonylation of a 2-(quinolin-8-yl)-2,3dihydro-1H-isoindole-1,3-dione led to the desired five-membered metallacycle. Each of these chapters represents the challenges to developing an oxidative decarboxylative arylation with unactivated C-H bonds with a first-row transition metal.
Decarbonylation
Metallacycle
Oxidative addition
Cite
Citations (0)
Palladium‐catalyzed amination of aryl halides is widely used in the synthesis of N ‐aryl amine derivatives. N ‐Aryl amines have important applications as pharmaceuticals, agricultural chemicals, and electronic materials. This chapter provides a summary of the mechanism, the optimal choice of catalyst, and the scope of this important reaction. Application to the arylation of ammonia, amines, amide derivatives, hydrazines, NH imines, and azoles are discussed. The strengths and limitations of the palladium‐catalyzed methodology are compared to nickel‐ and copper‐catalyzed amine arylation methods. Examples of the use of palladium‐catalyzed amine arylation in the synthesis of pharmaceutical intermediates and natural products are highlighted.
Amide
Cite
Citations (20)
Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
Carbon fibers
Cite
Citations (0)
Cite
Citations (0)
A Ni-catalyzed reductive deaminative arylation at unactivated sp3 carbon centers is described. This operationally simple and user-friendly protocol exhibits excellent chemoselectivity profile and broad substrate scope, thus complementing existing metal-catalyzed cross-coupling reactions to forge sp3 C–C linkages. These virtues have been assessed in the context of late-stage functionalization, hence providing a strategic advantage to reliably generate structure diversity with amine-containing drugs.
Chemoselectivity
Scope (computer science)
Cite
Citations (121)
Key words C−H functionalization - azaarylmethyl amines - palladium catalysis
Surface Modification
Cite
Citations (0)
Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
Carbon fibers
Cite
Citations (0)
An iron(II)-catalyzed cross dehydrogenative coupling of electron-rich arenes with diarylmethanes is reported. This reaction involves both a benzylic sp³ C-H and aromatic sp² C-H functionalization. The reaction proceeds regioselectively if the ortho-position of the anisole or thioanisole is already occupied.
Anisole
Thioanisole
Coupling reaction
Surface Modification
Cite
Citations (0)
Key words nickel catalysis - enantioselectivity - fluorine - heterocycles
Cite
Citations (0)