State Key Laboratory of Microbial Technology, Shandong University, Qingdao 266237, China.
Published: October 2024
AI Article Synopsis
Article Abstract
The stereoconvergent synthesis of a single stereoisomer from /-olefin mixtures remains one of the foremost challenges in organic synthesis. Herein, we describe a nickel-catalyzed stereoconvergent cross-coupling between - and -mixed monofluoroalkenes and alkenyl electrophiles, which allows the construction of C(sp)-C(sp) bonds. This defluorinative transformation offers facile access to various 1,3-dienes with -selectivity and good functional group tolerance. Preliminary mechanistic studies indicate that the reaction most likely proceeds through a migratory insertion/β-F elimination/isomerization process.
As a class of versatile building blocks, chiral benzylic boronic esters are important intermediates employed in modern organic chemistry. We describe herein the first stereoconvergent multicomponent cross-coupling reaction of vinyl boronates, alkyltrifluoroborates, and aryl halides through a dual photoredox/nickel catalysis methodology. This synergistic platform permitted the benign construction of various enantioenriched benzylic boronic esters with broad substrate tolerance and moderate to excellent enantioselectivity (up to 98:2 ) from commercially available starting materials.
The stereoconvergent synthesis of a single stereoisomer from /-olefin mixtures remains one of the foremost challenges in organic synthesis. Herein, we describe a nickel-catalyzed stereoconvergent cross-coupling between - and -mixed monofluoroalkenes and alkenyl electrophiles, which allows the construction of C(sp)-C(sp) bonds. This defluorinative transformation offers facile access to various 1,3-dienes with -selectivity and good functional group tolerance.
State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Frontiers Science Center for New Organic Matter, Nankai University, Tianjin 300071, China.
Stereoconvergent reactions enable the transformation of mixed stereoisomers into well-defined, chiral products─a crucial strategy for handling /-mixed olefins, which are common but challenging substrates in organic synthesis. Herein, we report a stereoconvergent and highly enantioselective method for synthesizing -homoallylic alcohols via the nickel-catalyzed reductive coupling of /-mixed 1,3-dienes with aldehydes. This process is enabled by an -heterocyclic carbene ligand characterized by -symmetric backbone chirality and bulky 2,6-diisopropyl -aryl substituents.
A nickel-catalyzed reductive dimerization of bromocyclobutenes to produce unusual and unprecedented cyclobutene dimers was developed. In a stereoconvergent procedure, various bromocyclobutenes were readily dimerized in good yields, with good diastereoselectivities and broad functional group tolerance. Notably, the presence of a carbonyl group in the starting material appears to dictate diastereoselectivity.
Nickel excels at facilitating selective radical chemistry, playing a pivotal role in metalloenzyme catalysis and modern cross-coupling reactions. Radicals, being nonpolar and neutral, exhibit orthogonal reactivity to nucleophilic and basic functional groups commonly present in biomolecules. Harnessing this compatibility, we delve into the application of nickel-catalyzed radical pathways in the synthesis of noncanonical peptides and carbohydrates, critical for chemical biology studies and drug discovery.
