Site-Selective Carbonylative Cyclization with Two Allylic C-H Bonds Enabled by Radical Differentiation.

Controlling the site-selectivity of C-H functionalization is of significant importance and a formidable undertaking in synthetic organic chemistry, motivating the continuing development of efficient and sustainable technologies for activating C-H bonds. However, methods that control the site-selectivity for double C-H functionalization are rare. We herein report a conceptually new method to achieve highly site-selective C-H functionalization by implementing a radical single-out strategy.

RcOST1L phosphorylates RcPIF4 for proteasomal degradation to promote flowering in rose.

Flowering is a vital agronomic trait that determines the economic value of most ornamental plants. The flowering time of rose (Rosa spp.) is photoperiod insensitive and is thought to be tightly controlled by light intensity, although the detailed molecular mechanism remains unclear.

Iron-catalyzed fluoroalkylative alkylsulfonylation of alkenes via radical-anion relay.

Transition metal-catalyzed reductive difunctionalization of alkenes with alkyl halides is a powerful method for upgrading commodity chemicals into densely functionalized molecules. However, super stoichiometric amounts of metal reductant and the requirement of installing a directing group into alkenes to suppress the inherent β-H elimination bring great limitations to this type of reaction. We demonstrate herein that the difunctionalization of alkenes with two different alkyl halides is accessible via a radical-anion relay with NaSO as both reductant and sulfone-source.

Construction of Bidentate Phosphines Enabled by Photoinduced Reductive Diphosphination of Alkenes.

The diphosphination of alkenes through a radical pathway offers a promising approach for the rapid construction of aryl bisphosphines. However, such a synthetic strategy has not been successfully applied to the preparation of alkyl bisphosphines, partially due to the difficulties in the generation of phosphorus-centered radicals from common alkyl phosphine compounds. We herein demonstrate that this challenge can be overcome by hiring Janus-faced chlorophosphine as the phosphine source that can act as not only a radical precursor to generate phosphine-centered radicals but also a radicalphile to capture alkyl radicals.

Intramolecular Carboamination of Aminodienes to N-Heterocycles via C-N Bond Activation.

The catalytic transformation of ubiquitous but inert C-N bonds is highly appealing in synthetic chemistry, but the efficient cleaving inert C-N bond and simultaneous incorporation of both the cleaved C-moiety and N-moiety into the desired products has been a long-standing formidable challenge so far. Here, we developed a radical-addition triggered cyclization and C-N bond cleavage process enabled by the unique I /Ni or benzyl halide/Ni-catalytic system, allowing the formal insertion of diene into the inert C-N bond. This reaction features high atom economy and enables an expedient annulative carboamination of aminodienes to diverse pyrrolidines, piperidines, and tetrahydroisoquinolines.

Unlocking a self-catalytic cycle in a copper-catalyzed aerobic oxidative coupling/cyclization reaction.

Presented here is a copper-catalyzed, aerobic oxidative C-H/C-H cyclization reaction, which occurs by cleaving the C-H and N-H bonds of 3-phenylindoles. A broad range of 3-phenylindoles can be well tolerated to produce the indole-containing polycyclic aromatic hydrocarbons (PAH) in good to excellent yields. An evaluation of the reaction mechanism is enabled by the isolation of the di- and tri-indole intermediates, highlighting the role of the substrate for this catalytic reaction.

Palladium-Catalyzed Ring-Closing Reaction via C-N Bond Metathesis for Rapid Construction of Saturated -Heterocycles.

The ring-closing reactions based on chemical bond metathesis enable the efficient construction of a wide variety of cyclic systems which receive broad interest from medicinal and organic communities. However, the analogous reaction with C-N bond metathesis as a strategic fundamental step remains an unanswered challenge. Herein, we report the design of a new fundamental metallic C-N bond metathesis reaction that enables the palladium-catalyzed ring-closing reaction of aminodienes with aminals.

Catalytic Claisen Rearrangement by Intercepting Ketenimines with Propargylic Alcohols: A Strategy to Generate and Transform Ketenimines from Radicals.

An efficient strategy for facilitating the cross-coupling of two radicals has been established via the coordination of a radical with a metal catalyst. This strategy provides a remarkable ability to harness the reactivity of nitrile-containing azoalkanes and enables a novel cascade reaction with nitrile-containing azoalkanes and propargylic alcohols to be established. By using this reaction, a range of acetylenic and allenic amides were obtained that provides a versatile platform for further derivatizations.

Synthesis and Characterization of Rh/B⁻TNTs as a Recyclable Catalyst for Hydroformylation of Olefin Containing ⁻CN Functional Group.

The TiO₂-based nanotubes (TNTs, B⁻TNTs) of different surface acidities and their supported Rh catalysts were designed and synthesized. The catalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectrometer (XPS), tempera⁻ture⁻programmed desorption of ammonia (NH₃⁻TPD), atomic emission spectrometer (ICP), and Brunauer⁻Emmett⁻Tellerv (BET) surface-area analyzers. Images of SEM and TEM showed that the boron-decorated TiO₂ nanotubes (B⁻TNTs) had a perfect multiwalled tubular structure; their length was up to hundreds of nanometers and inner diameter was about 7 nm.