An unprecedented palladium (Pd)‑catalyzed insertion of unsaturated carbenes into B─H bonds is described. Using alkynyl hypervalent iodine reagents as carbene precursors and amine-borane adducts as boron sources, this method delivers a broad range of E‑configured alkenyl monoborinates in good-to-high yields with exceptional stereoselectivity (>20:1 E/Z). The reaction proceeds under mild conditions, tolerates diverse aromatic, heteroaromatic, and aliphatic substituents, and is readily scalable to gram quantities. The resulting monoboronate products participate efficiently in a variety of C─X bond‑forming transformations, underscoring their synthetic versatility. Initial mechanistic investigations and DFT calculation support the formation of an unsaturated Pd-vinylidene intermediate, with stereocontrol influenced by ligand coordination at the palladium center. Collectively, this work establishes a mechanistic and conceptual bridge between unsaturated carbene chemistry and organoboron synthesis, expanding the reactivity landscape of Pd‑-carbene intermediates.
Herein, we report a palladium-catalyzed 1,2-carboamination of acrylamides via anti-Michael-type addition. The protocol enables reverse regioselective functionalization of activated alkenes using carbazole derivatives as nucleophiles and aryl, vinyl, and alkyl iodide derivatives as electrophiles under mild reaction cond...
S. Singh, M. Jeganmohan· Organic Letters· 0 citations
A palladium-catalyzed (3 + 2) cycloaddition between arylalkynes and norbornene derivatives via C–H bond cleavage is reported. This reaction enables the selective synthesis of benzo-fused five-membered cyclic products from a variety of arylalkynes, including electronically biased and alkyl(aryl)alkynes. Notably, the u...
Sakura Takahashi, M. Tobisu, Y. Ano· ACS Catalysis· 0 citations
Direct activation of native C(sp2)–NH2 bonds in alkenyl amines remains a largely unmet challenge in cross-coupling chemistry owing to their high bond dissociation energies, poor leaving-group ability, and competing tautomerization pathways. Herein, we report a nickel-catalyzed tandem deaminative coupling/alkene isome...
Although boron compounds appear in many chemical transformations, it is hard to imagine, these usually Lewis acidic, species would act as Lewis bases or even base-catalysts. Here we show that the adduct o-2, formed by the reaction of closo−1,2-dicarbadecaborane(10) with two equivalents of an N-heterocyclic carbene, exh...
Jan Vrána, Zuzana Kapustová, M. Kamlar et al.· Nature Communications· 0 citations
Selective synthetic routes to prepare boronic esters are highly desirable as they are valuable intermediates in the preparation of pharmaceuticals, agrochemicals, and functional materials. In this paper, we report an approach to generate boronic esters through the ring-opening hydroboration of benzylidene cyclobutane...
Wen-Bang Yang, Joseph M. Parr, Esther Raga et al.· ACS Catalysis· 1 citation
