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The catalytic asymmetric synthesis of axially chiral alkenes remains a challenge due to the lower rotational barrier, especially for longer stereogenic axis. Here the authors report a nickel-catalyzed atroposelective radical relayed reductive coupling reaction of ethynyl-azaborines with alkyl/aryl halides through a boron-stabilized vinyl radical intermediate.

Chiral 1,2-benzazaborines are promising isosteres of naphthalene, but rarely explored due to the lack of efficient synthetic methods. Now, the copper-catalysed enantioselective hydroboration of alkenes with 1,2-benzazaborines has been developed, providing a general platform for the atom-economic and efficient construction of diverse chiral 1,2-benzazaborine compounds bearing a 2-carbon-stereogenic centre or allene skeleton.

The 1,2 migration reaction on tetracoordinate boron species have been well investigated but less work looked on 1,2-boryl radical shift for the construction of organoborons. Here, the authors demonstrate a visible-light-induced photoredox neutral decarboxylative radical cross-coupling reaction, which undergoes a radical 1,2-boron shift to give a translocated C-radical for further capture of versatile radical acceptors

The application of catalytic dynamic kinetic asymmetric transformation (DyKAT) in axial chirality is limited to fivemembered metalacyclic intermediate-directed equilibrium of substrate enantiomers. Here, the authors report a tetracoordinate boron-directed DyKAT of racemic, configurationally stable 3-bromo- 2,1-azaborines for the construction of C-B axial chirality.

Multicomponent reactions enable the rapid construction of diverse molecular scaffolds with modularity and step economy. In this work, the authors report the use of boronic acids as carbon nucleophiles in a Passerini-type three-component coupling reaction towards an expanded inventory of α-hydroxyketones.

Ribosome biogenesis is crucial for maintaining stem cell homeostasis. Here, authors reveal that DDX10 plays a critical role in ribosome biogenesis by regulating 18S rRNA maturation, which is vital for the proliferation and maintenance of mESCs.

The conventional method for synthesizing thioether compounds typically relies on thiol, disulfide, and sulfinyl halide as initial substances, suffering from strong odors, limited availability, and reactivity issues. Here, the authors present an approach for assembling S-thiosulfonates and SS-thiosulfonates through the integration of dual copper/photoredox catalysis

The Stevens rearrangements are a fundamental and powerful tool in the synthetic organic chemistry repertoire, but these transformations are known to be limited in their tolerance for some common functional groups. Here, the authors present a methodology that uses a difluorocarbene unit to induce a Stevens rearrangement, which enables smooth inclusion of allylic and propargyl moieties in the transformation.

Multi-component cascade transformations including difunctionalization of two alkynes with both syn- and anti-selectivity in one catalyst system is challenging. Herein, the authors report a Nickel-catalyzed four-component reaction to access densely substituted 1,3-dienes using two terminal alkynes, aryl boroxines, and perfluoroalkyl iodides.

Suzuki-type cross-coupling for C(sp²)–C(sp³) bond formation with aliphatic halides remains challenging with tertiary aliphatic halides and under transition-metal-free conditions. Now, a transition-metal-free C(sp²)–C(sp³) cross-coupling of α-(pseudo)halo aliphatic ketones with boronic acids via a 1,4-metallate shift is reported which is compatible with tertiary aliphatic halides, allowing for 1,3-disubstituted products.

Enantioselective transformations based on tetracoordinate borons are elusive. Now, an enantioselective nickel-catalysed strategy for the construction of axially chiral alkenes has been reported, via a 1,3-metallate shift of alkynyl tetracoordinate boron species. The reaction uses readily accessible starting materials and a cheap transition-metal catalyst, and the chemoselectivity, regioselectivity and atroposelectivity could be well controlled.

A combined copper- and palladium-catalysed atropselective arylboration of alkynes is reported. This method uses B₂pin₂ and sterically hindered aryl bromides for the stereoselective and regioselective synthesis of axially chiral tetrasubstituted alkenylboronates. Mechanistic studies reveal that the stereocontrol originates from a higher-order palladium intermediate.

Optically enriched 1,1-diboron compounds are significantly underdeveloped because of the paucity of the straightforward synthetic protocols. Herein, the authors report an enantioselective copper-catalyzed cascade double hydroboration of terminal alkynes to access highly enantioenriched gem-diborylalkanes.

Tetracoordinate boron species are common radical precursors in organic synthesis, but the boron species are discarded as by-products. Herein the authors report a strategy to incorporate both the alkyl moiety and boron species into the eventual products, yielding organoboron compounds.

Enantioselective catalytic methods for the construction of boron-stereogenic compounds are elusive. In this article, the authors describe a route to these compounds via a copper-catalysed desymmetric B-H insertion on 2-arylpyridine-boranes with carbenes.

2-Fluoroindoles are an important structural scaffold in many bioactive or therapeutic agents, but efficient constructions of 2-fluoroindole derivatives are very sparce. Here the authors report an efficient and general strategy for the construction of 2-fluoroindoles in which a wide variety of 2-fluoroindoles were accessed with high efficiency and chemoselectivity.

Alternative carbene precursors for metal-catalyzed cross coupling may expand the portfolio of methods for C-C bond construction. Here, the authors report a Suzuki−Miyaura coupling of Pd−carbene complexes formed by desulfurization of thioureas or thioamides and affording a broad array of amidinium salts and diaryl ketones.