The first enantioselective decarboxylative [4 + 2]-annulation of ethynyl benzoxazinanones with azlactones has been developed under cooperative copper and bifunctional tertiary aminourea catalysis. This direct modular approach combines dipolar copper-allenylidene intermediates azlactone enolates allows for the synthesis α-quaternary α-acylaminoamides as a single diastereomer generally in high yields good to excellent enantioselectivities (up 99:1 er).

A method to achieve the synthesis of highly substituted spirocyclic cyclobutanes is disclosed. The reaction involves catalytic arylboration cyclobutenes. Depending on substitution pattern cyclobutene, either a Cu/Pd- or Ni-catalyzed was utilized. In case Cu/Pd catalyzed reactions, identification Cu-complex for crucial observe high selectivity. synthetic utility products demonstrated, and mechanistic details are discussed.

The catalytic enantioselective synthesis of α-chiral alkenes and alkynes represents a powerful strategy for rapid generation molecular complexity. Herein, we report transient directing group (TDG) to facilitate site-selective palladium-catalyzed reductive Heck-type hydroalkenylation hydroalkynylation alkenylaldehyes using alkenyl alkynyl bromides, respectively, allowing construction stereocenter at the δ-position with respect aldehyde. Computational studies reveal dual beneficial roles rigid...

A formal γ-allylation of deconjugated butenolides is reported based on a two-step sequence consisting catalytic diastereo- and enantioselective vinylogous nucleophilic addition to vinyl sulfones Julia-Kocienski olefination. This highly modular approach delivers densely functionalized containing quaternary stereogenic centre in excellent yield with high enantioselectivity.

General visible light-mediated aerobic oxidation of boronic acids is unveiled using CdSe nanocrystal quantum dots (QDs) as the photoredox catalyst. This protocol requires mild reaction conditions and low catalyst loading (down to 10 ppm), tolerates various functional groups. The resulting phenols aliphatic alcohols are produced in good high yield with turnover numbers >62000. mechanism probed ultrafast transient absorption luminescence spectroscopy. existence a rapid 350 ps initial electron...

A highly enantioselective cascade sulfa-Michael/Julia–Kocienski olefination reaction between 2-mercaptobenzaldehydes and β-substituted vinyl PT-sulfones has been realized for the synthesis of 3,4-unsubstituted 2H-thiochromenes. This reaction, catalyzed by diphenylprolinol TMS ether, proceeds through an aromatic iminium intermediate furnishes a wide range 2-substiuted 2H-thiochromenes with excellent enantioselectivities (up to 99:1 er).

We synthesized CuAlS2/ZnS quantum dots (QDs) composed of biocompatible, earth-abundant elements that can reduce salts carbon dioxide under visible light. The use an asymmetric morphology at a type-II heterointerface balances multiple requirements photoredox agent by providing low optical bandgap (∼1.5 eV), large cross section (>10–16 cm2 above 1.8 spatial proximity both semiconductor components to the surface, as well photochemical stability. QDs thus have unprecedented activity in terms...

The first catalytic enantioselective synthesis of 5,6-dihydro-4H-1,2-oxazines bearing an oxygen-containing quaternary stereogenic center has been developed through iodoetherification γ,δ-unsaturated oximes. This operationally straightforward reaction is catalyzed by Cinchona alkaloids-based bifunctional tertiary aminothiourea derivatives and furnishes the products generally in good to excellent yields with moderate high enantioselectivities (up 97:3 er).

We report a redox-neutral catalytic coupling of nitroalkanes and unactivated alkenes that proceeds by directed carbopalladation mechanism. The reaction is uniquely enabled the combination PdI2 as precatalyst HFIP solvent. Structurally complex nitroalkane products, including nitro-containing carbo- heterocycles, are prepared under operationally convenient conditions without need for toxic or corrosive reagents. Deuterium labeling experiments isolation catalytically relevant intermediate shed...

Abstract A process to achieve 1,2‐metalate rearrangements of indole boronate as a way access substituted indolines in high diastereoselectivities is presented. The reaction involves the generation Cu–allenylidene, which sufficiently electrophilic induce rearrangement. scope evaluated well further transformations product.

Through the combination of a Ni-catalyzed alkene alkenylboration followed by hydrogenation, synthesis congested Csp³–Csp³-bonds can be achieved.

Abstract CuAlS 2 /ZnS Quantum dots (QDs) are known to directly convert aqueous solutions of bicarbonate ions oxygen and organic molecules such as formate with a remarkable efficiency even under sunlight. In cases, fairly complicated reaction products acetate methanol have been observed when reactions allowed continue for longer periods time. Here, we investigate the electron dynamics that occurs within QDs show it is essentially dominated by ultrafast transfer (560 fs 0.4 excitons per dot)...

Abstract A process to achieve 1,2‐metalate rearrangements of indole boronate as a way access substituted indolines in high diastereoselectivities is presented. The reaction involves the generation Cu–allenylidene, which sufficiently electrophilic induce rearrangement. scope evaluated well further transformations product.

Abstract based on a two‐step protocol involving catalytic diastereo‐ and enantioselective vinylogous nucleophilic addition to vinyl sulfones Julia—Kocienski olefination

Abstract The catalytic enantioselective synthesis of α‐chiral alkenes and alkynes represents a powerful strategy for rapid generation molecular complexity. Herein, we report transient directing group (TDG) to facilitate site‐selective palladium‐catalyzed reductive Heck‐type hydroalkenylation hydroalkynylation alkenylaldehyes using alkenyl alkynyl bromides, respectively, allowing construction stereocenter at the δ‐position with respect aldehyde. Computational studies reveal dual beneficial...