Catalyst-Controlled Direct Oxysulfonylation of Alkenes by Using Sulfonylazides as the Sulfonyl Radical

A copper/cobalt-catalyzed difunctionalization of alkenes with sulfonylazides and tert-butyl hydroperoxide has been achieved. This protocol provides an efficient and direct oxysulfonylation approach to β-ketosulfones and β-sulfonyl peroxides in moderate to good yields under mild conditions. This methodology applies sulfonylazides as a new sulfonyl radical source and features a wide substrate scope and good functional group tolerance

Assessment of Amino Acid Neurotransmitters in Rat Brain Microdialysis Samples by High-Performance Liquid Chromatography with Coulometric Detection

<div><p>A simple method was developed for simultaneous determination of five amino acid neurotransmitters (taurine, glutamate, aspartate, glycine, and γ-aminobutyric acid) in brain microdialysates by high-performance liquid chromatography with coulometric detection. The microdialysates were derivatized with <i>o</i>-phthalaldehyde in 5 mM sodium sulfite and separated within 17 min using isocratic elution. Detection parameters for these transmitters were linearity (<i>r</i>²) > 0.999 over the concentration range from 0.1 to 15.00 µM (0.01–1.00 µM for GABA); reproducibility 2.88%–11.67% (relative standard deviation); the limits of detection 4.4–17.2 fmol; and recovery 86.66%–103.42%. This method was successfully applied to analyze these neurotransmitters in the brain. The changes of neurotransmitters were also investigated via local administration of potassium chloride and bicuculline, which was a γ-aminobutyric acid receptor antagonist. It was found that the developed method is more efficient as compared to previously reported methods in simultaneously determining five major neurotransmitters because it shows quick separation and sensitive detection, and is easy to operate. This method can be a practical choice for continuous monitoring of the amino acid neurotransmitters<i>in vivo</i>.</p></div

TBAI-Catalyzed S–H and N–H Insertion Reactions of α‑Diazoesters with Thiophenols and Amines under Metal-Free Conditions

Mild, convenient, and effective TBAI-catalyzed S–H and N–H insertion reactions of α-diazoesters with thiophenols and aromatic amines under metal-free conditions have been described, furnishing a straightforward and general platform for the synthesis of various thioethers and 2-amino-2-oxoacetates in moderate to excellent yields. Moreover, this strategy features simple operation, mild conditions, broad substrate scope, and easy scale-up

Synthesis of γ‑Lactones by TBAI-Promoted Intermolecular Carboesterification of Carboxylic Acids with Alkenes and Alcohols

A novel tetrabutylammonium iodide (TBAI)-promoted three-component reaction of carboxylic acid with alkene and alcohol has been developed, which represents facile and straightforward access to polysubstituted γ-lactone skeletons in moderate-to-good yields. This methodology is distinguished by the use of a commercial catalyst and readily available starting materials, wide substrate scope, and operational simplicity. Mechanistic studies suggested that this transformation went through a radical process

Copper-Catalyzed Regio- and Stereoselective Sulfonylation of Alkynyl Imines with Sulfonyl Hydrazides: Access to (<i>E</i>)‑β-Sulfonyl Enones

A copper-catalyzed sulfonylation of alkynyl imines with sulfonyl hydrazides has been developed, which exhibited excellent regio- and stereoselectivity and furnished a series of (E)-β-sulfonyl enones in moderate to good yields. Mechanistic studies suggest that this strategy goes through a radical process

Substrate-Controlled Regioselectivity Switchable [3 + 2] Annulations To Access Spirooxindole Skeletons

The additive-free [3 + 2] annulation from isatins, amino acids with 2-styrylbenzoxazoles, was described, providing a series of functional and structurally complex 3,3′-pyrrolidinyl-spirooxindole derivatives containing four contiguous and two quaternary stereogenic centers in high yields (up to 95%) and excellent diastereoselectivities (up to >25:1 dr). Interestingly, the reaction exhibits switchable regioselectivity depending on the substrate of amino acids. With proline or thioproline as the substrate, the reaction afforded α-regioselective spirooxindole skeletons. In contrast, when piperidine acid is the substrate, the reaction provided γ-regioselective spirooxindole skeletons

Substrate-Controlled Regioselectivity Switchable [3 + 2] Annulations To Access Spirooxindole Skeletons

The additive-free [3 + 2] annulation from isatins, amino acids with 2-styrylbenzoxazoles, was described, providing a series of functional and structurally complex 3,3′-pyrrolidinyl-spirooxindole derivatives containing four contiguous and two quaternary stereogenic centers in high yields (up to 95%) and excellent diastereoselectivities (up to >25:1 dr). Interestingly, the reaction exhibits switchable regioselectivity depending on the substrate of amino acids. With proline or thioproline as the substrate, the reaction afforded α-regioselective spirooxindole skeletons. In contrast, when piperidine acid is the substrate, the reaction provided γ-regioselective spirooxindole skeletons

Divergent Synthesis of Highly Substituted Tetrahydroquinolines and Cyclopentenes via Lewis Base Catalyzed Switchable [4 + 2] and [3 + 2] Annulations of MBH-Carbonates with Activated Olefins

A highly selective and divergent synthesis which enabled access to various complex compounds is highly attractive in organic synthesis and medicinal chemistry. Herein, we developed an effective method for divergent synthesis of highly substituted tetrahydroquinolines via Lewis base catalyzed switchable annulations of Morita–Baylis–Hillman carbonates with activated olefins. The reaction displayed switchable [4 + 2] or [3 + 2] annulations via catalyst or substrate control, providing a diverse range of architectures which contained highly substituted tetrahydroquinolines or cyclopentenes with three contiguous stereocenters bearing a quaternary carbon center in high yields with excellent diastereoselectivities and regioselectivities. Furthermore, synthetic utility of this strategy was further highlighted by gram-scale experiments and simple transformations of the products