Correction to Synthesis of Heterocycles via Pd-Ligand Controlled Cyclization of 2‑Chloro‑<i>N</i>‑(2-vinyl)aniline: Preparation of Carbazoles, Indoles, Dibenzazepines, and Acridines

Correction to Synthesis of Heterocycles via Pd-Ligand Controlled Cyclization of 2‑Chloro‑<i>N</i>‑(2-vinyl)aniline: Preparation of Carbazoles, Indoles, Dibenzazepines, and Acridine

Ligand-Controlled Palladium-Catalyzed Regiodivergent Suzuki–Miyaura Cross-Coupling of Allylboronates and Aryl Halides

An orthogonal set of catalyst systems has been developed for the Suzuki–Miyaura coupling of 3,3-disubstituted and 3-monosubstituted allylboronates with (hetero)­aryl halides. These methods allow for the highly selective preparation of either the α- or the γ-isomeric coupling product

Versatile Enantioselective Synthesis of Functionalized Lactones via Copper-Catalyzed Radical Oxyfunctionalization of Alkenes

A versatile method for the rapid synthesis of diverse enantiomerically enriched lactones has been developed based on Cu-catalyzed enantioselective radical oxyfunctionalization of alkenes. The scope of this strategy encompasses a series of enantioselective difunctionalization reactions: oxyazidation, oxysulfonylation, oxyarylation, diacyloxylation, and oxyalkylation. These reactions provide straightforward access to a wide range of useful chiral lactone building blocks containing tetrasubstituted stereogenic centers, which are hard to access traditionally

Correction to Synthesis of Heterocycles via Pd-Ligand Controlled Cyclization of 2‑Chloro‑<i>N</i>‑(2-vinyl)aniline: Preparation of Carbazoles, Indoles, Dibenzazepines, and Acridines

Correction to Synthesis of Heterocycles via Pd-Ligand Controlled Cyclization of 2‑Chloro‑<i>N</i>‑(2-vinyl)aniline: Preparation of Carbazoles, Indoles, Dibenzazepines, and Acridine

Regioselective 2‑Amination of Polychloropyrimidines

The regioselective amination of substituted di- and trichloropyrimidines affording the 2-substituted products is reported. While aryl- and heteroarylamines require the use of a dialkylbiarylphosphine-derived palladium catalyst for high efficiency, more nucleophilic dialkylamines produce 2-aminopyrimidines under noncatalyzed S_NAr conditions. The key is the use of 5-trimethylsilyl-2,4-dichloropyrimidine as a surrogate for the parent dichloropyrimidine. For more challenging cases, the 2-chloro-4-thiomethoxy analogues were prepared and exclusively afford the desired 2-aminated-4-thiomethoxypyrimidine products

Enantioselective CuH-Catalyzed Anti-Markovnikov Hydroamination of 1,1-Disubstituted Alkenes

Enantioselective synthesis of β-chiral amines has been achieved via copper-catalyzed hydro­amination of 1,1-disubstituted alkenes with hydroxylamine esters in the presence of a hydrosilane. This mild process affords a range of structurally diverse β-chiral amines, including β-deuterated amines, in excellent yields with high enantio­selectivities. Furthermore, catalyst loading as low as 0.4 mol% could be employed to deliver product in undiminished yield and selectivity, demonstrating the practicality of this method for large-scale synthesis

Continuous-Flow Preparation and Use of β‑Chloro Enals Using the Vilsmeier Reagent

The Vilsmeier reagent is used in the preparation of a wide variety of heterocycles, such as pyrazoles, <i>via</i> formation of β-chloroacrolein intermediates. However, use of this extremely reactive reagent on large scale requires special precautions to avoid potentially dangerous exotherms. This article describes the safe preparation at room temperature of the Vilsmeier reagent under flow conditions for the formation of β-chloroacroleins and 3-formylchromones, as well as the use of these in multistep, continuous flow processes for the syntheses of β-acrylonitriles and polysubstituted pyrazoles

Continuous-Flow Synthesis of Monoarylated Acetaldehydes Using Aryldiazonium Salts

Anilines and ethyl vinyl ether can be used as precursors for a process that is the synthetic equivalent of the α-arylation of acetaldehyde enolate. The reaction manifests a high level of functional group compatibility, allowing the ready preparation of a number of synthetically valuable compounds

Correction to Continuous-Flow Synthesis of Monoarylated Acetaldehydes Using Aryldiazonium Salts

Correction to Continuous-Flow Synthesis of Monoarylated Acetaldehydes Using Aryldiazonium Salt

Synthesis of Optically Pure 2‑Trifluoromethyl Lactic Acid by Asymmetric Hydroformylation

By utilizing Rh catalysts ligated by the <i>P</i>-chirogenic ligands QuinoxP* and DuanPhos, 3,3,3-trifluoroprop-1-en-2-yl acetate could be hydroformylated and subsequently oxidized to yield enantiomerically pure 2-trifluoromethyllactic acid