Titanium catalyzed [2σ + 2π] cycloaddition of bicyclo[1.1.0]-butanes with 1,3-dienes for efficient synthesis of stilbene bioisosteres.

Natural stilbenes have shown significant potential in the prevention and treatment of diseases due to their diverse pharmacological activities. Here we present a mild and effective Ti-catalyzed intermolecular radical-relay [2σ + 2π] cycloaddition of bicyclo[1.1.0]-butanes and 1,3-dienes. This transformation enables the synthesis of bicyclo[2.1.1]hexane (BCH) scaffolds containing aryl vinyl groups with excellent regio- and trans-selectivity and broad functional group tolerance, thus offering rapid access to structurally diverse stilbene bioisosteres.

Hantzsch Esters Enabled [2π+2σ] Cycloadditions of Bicyclo [1.1.0] butanes and Alkenes under Photo Conditions.

Hantzsch esters (HEs) are widely recognized as sources of hydride ions (H-) and sacrificial electron donors in their ground state. Here, we report the application of HE as a mediator in [2π+2σ] cycloaddition of bicyclo[1.1.0]butanes (BCBs) with alkenes under photo conditions. Through this strategy, various substituted bicyclo[2.1.1]hexanes can be efficiently prepared.

Radical Crotylation of Aldehydes with 1,3-Butadiene by Photoredox Cobalt and Titanium Dual Catalysis.

Metal-hydride hydrogen atom transfer (MHAT) has been recognized as a powerful method for alkene functionalization; however, photochemical MAT-mediated chemoselective functionalization of dienes remains undeveloped. In this study, we report a radical strategy (1e-) through MHAT using photoredox cobalt and titanium dual catalysis for aldehyde crotylation with butadiene, achieving excellent regio- and diastereoselectivity.

Photoinduced copper-catalyzed selective three-component 1,2-amino oxygenation of 1,3-dienes.

This study presents a highly effective method for the photoinduced copper-catalyzed 1,2-amino oxygenation of 1,3-dienes. This synthetic strategy involves the dual roles of a single copper catalyst, which can act as a photosensitizer to generate nitrogen radicals and can also react with allyl radicals via single electron transfer (SET) processes. The method produces a range of quaternary carbon-centered allyl carboxylic esters and tertiary ethers with high yields and excellent regioselectivity under mild reaction conditions.

Difunctionalization of 1,3-Butadiene via Sequential Radical Thiol-ene Reaction and Allylation by Dual Photoredox and Titanium Catalysis.

Recently, radical difunctionalization of the feedstock 1,3-butadiene has become an attractive strategy for increasing molecular complexity. Herein, we present a novel approach that effectively combines radical thiol-ene chemistry with TiIII catalysis to enable a three-component aldehyde allylation using 1,3-butadiene as an allyl group source under visible light conditions. This sustainable and straightforward method has facilitated the rapid production of diverse allylic 1,3-thioalcohols with exceptional regio- and diastereoselectivity.

Photocatalytic Metal Hydride Hydrogen Atom Transfer Mediated Allene Functionalization by Cobalt and Titanium Dual Catalysis.

Catalytic metal hydride hydrogen atom transfer (MHAT) reactions have proven to be a powerful method for alkene functionalization. This work reports the discovery of Co-porphines as highly efficient MHAT catalysts with a loading of only 0.01 mol % for unprecedented chemoselective allene functionalization under photoirradiation. Moreover, the newly developed bimetallic strategy by the combination of photo Co-MHAT and Ti catalysis enabled the successful carbonyl allylation with a wide range of amino, oxy, thio, aryl, and alkyl-allenes providing expedient access to valuable ß-functionalized homoallylic alcohols in over 100 examples with exceptional regio- and diastereoselectivity. Mechanism studies and DFT calculations supported that selectively transferring hydrogen atoms from cobalt hydride to allenes and generating allyl radicals is the key step in the catalytic cycle.

Synthesis of Homoallylic Amines by Radical Allylation of Imines with Butadiene under Photoredox Catalysis.

Ionic (2 e- ) nucleophilic addition of allylmetal regents to imines dominates the synthesis of homo-allyl amine; however, single electron (1 e- ) mediated imine allylation with feedstocks butadiene as an alternative allyl source remains unexplored. In this work, we report a conceptually different radical-radical cross-coupling strategy for the synthesis of a homoallyl amine between an α-amino alkyl radical and a transient allylic radical. This metal-free method provided a novel approach for the synthesis of homoallylic amines (>80 examples) from readily available materials with excellent regioselectivity and exceptional broad functional group compatibility.

Activation of Chromium Catalysts by Photoexcited Hantzsch Ester for Decarboxylative Allylation of Aldehydes with Butadiene.

Metallaphotocatalysis often needs light-absorbing metal-polypyridyl complexes, semiconductors, or organic dyes, which can modify the oxidation state of metal catalysts. Here, we first report that photoexcitation of Hantzsch ester can directly activate chromium reagents through a single-electron transfer process. The synthetic application was demonstrated through a photoredox decarboxylative allylation of aldehydes with feedstock butadiene without exogenous photocatalysts, metallic reductants, or additives.

Photocatalytic Generation of π-Allyltitanium Complexes via Radical Intermediates.

The addition of π-allylmetal complexes to carbonyls is the most important route to homoallylic alcohols. This study reports the first photocatalytic generation of π-allyltitanium complexes by a radical strategy. This novel strategy enables the three-component allylation of carbonyls with 1,3-butadiene, providing rapid access to valuable homoallylic alcohols (over 60 examples). The exceptional regio- and diastereoselectivity provided by dual photoredox/Ti catalysis is comparable to that of the Cr-catalyzed Nozaki-Hiyama-Kishi allylation reaction.