A microwave-assisted, Cp*CoIII-catalyzed direct C–H activation/double C–N bond formation reaction of simple NH-sulfoximines with 1,4,2-dioxazol-5-ones to produce diverse thiadiazine-1-oxides is reported. The tolerates a broad range functional groups under external oxidant-free conditions and only releases CO2 H2O as the sole byproducts. preliminary mechanistic studies revealed an electrophilic metalation pathway likely involved in reaction.

Abstract From the viewpoint of synthetic accessibility and functional group compatibility, photoredox-catalyzed sulfur dioxide insertion strategy enables in situ generation functionalized sulfonyl radicals from easily accessible starting materials under mild conditions, thereby conferring broader application potential. Here we present two complementary photoinduced systems to trigger radical asymmetric Truce–Smiles rearrangements for preparing a variety chiral sulfones that bear quaternary...

This review summarizes the growing landscape in reactions of silacyclobutanes (SCBs) by highlighting fascinating progress, deconstructing mechanistic underpinnings, and drawing insight from related ring-opening expanding SCBs.

A photoredox-catalyzed reaction of thianthrenium salts, hydrazines and DABCO·(SO 2 ) is accomplished, providing diverse arenesulfonohydrazides in moderate to good yields under mild conditions.

Abstract Decyanation is an important process in the synthesis of aromatic molecules studies pharmaceutical research, medical and materials sciences. In late‐stage modifications privileged carbo/heterocyclic scaffolds, radical‐type decyanation techniques have been devised to date. As a result, chemistry cyano‐involved conversions, hotly debated subject over past few decades, has advanced significantly. The cyano group (CN), on other hand, rarely acknowledged as good reaction site due its...

Significant progress in the chemistry of nitro radicals has been witnessed past decades, providing efficient and rapid access to nitro-containing compounds. This review describes recent advances nitro-involved radical reactions, summarizes various transformations.

A simple and low-cost tandem sulfonylation/cyclization of 1,5-diene, aryldiazonium salt, DABCO·(SO2)2 is disclosed. This base-promoted multicomponent reaction can provide a "green" economic synthesis sulfonylated pyrrolidones under transition-metal-free moisture/oxygen-insensitive conditions, thus delivering wide range in moderate to high yields with excellent functional group compatibility. plausible mechanism involving radical process proposed, which demonstrates highly chemoselective...

Abstract Under heating conditions, an iron(II)‐catalyzed cascade cyanoalkylsulfonylation/cyclization reaction is developed to produce cyanoalkylsulfonylated pyrrolidones bearing with a free CN moiety. This alkyl radical disconnection and annulation protocol enjoys chemo‐ regioselectivity the tolerance toward range of functional groups. The reactive cyanoalkyl radical, which was originated from ring‐opening cyclic imine found be capable capturing in‐situ generated “SO 2 ” species DABSO, thus...

Abstract Over the past few years, substantial progress has been achieved in nitroso‐related organic chemistry. Annulation reactions of nitroso compounds with other π‐conjugated systems, particular through notable hetero‐Diels–Alder‐type reaction, have drawn much interest from chemists because their high regioselectivities, enantioselectivities, and efficiencies. In addition, N ‐nitroso moiety can also be employed as a powerful transformable directing group direct C−H functionalization...

Methylation is an important process in biology. To date, radical-type methylation protocols have been developed the late-stage modifications of privileged scaffolds pharmaceutical research and medicinal materials sciences. As a result, chemistry methyl-radical-involved conversions, which was significant topic interest over past few years, has greatly developed. This review focuses on most recent developments catalytic radical or demethylation that were mediated by methyl radicals. We...

A multi-component reaction of electron-rich arenes, potassium metabisulfite, aldehydes and aryldiazonium tetrafluoroborates under mild conditions is reported, leading to a range (arylsulfonyl)methylbenzenes in moderate good yields.

An iron(<sc>ii</sc>)-catalyzed three-component reaction of <italic>O</italic>-acyl oximes, sulfur dioxide, and <italic>N</italic>-vinylacetamides is accomplished. Diverse (<italic>E</italic>)-β-sulfonyl enamines are obtained in moderate to good yields by using this protocol with excellent stereoselectivity regioselectivity.

Disclosed herein is a novel Rh/Ag co-catalyzed SNH directed C–H activation and C–H/N–H bond functionalization protocol of free NH-sulfoximines with hypervalent iodonium ylides. With the aid AgOTf, these functionalization/cyclization sequences could be achieved at room temperature conditions. The reaction employed EtOH as "green" solvent low catalyst loading was required under an oxygen/water-insensitive condition. Under this mild protocol, wide range polyheterocyclic sulfoximines bearing...

We report herein a Au/Ag-cocatalyzed chemoselective hydrosulfoximination reaction of simple ynamides with free NH-sulfoximines, which produces the N-alkenylated sulfoximidoyl derivatives quantitative atom efficiency and good to excellent yields. Further elaborations enamine isomers under Ru-catalyzed oxidative conditions cleave C═C double bonds can selectively afford urea-type sulfoximines. The aforementioned catalytic reactions provide new opportunities for convergent straightforward access...

An efficient route to γ-keto sulfones through a metal-free reaction of cyclopropanols, sulfur dioxide and electron-deficient olefins is achieved. This proceeds smoothly under mild conditions without the need catalyst, oxidant or additive.

As the aza-analogues of sulfoxides, sulfilimines bearing S(IV) stereogenic centers hold tremendous potential in synthetic chemistry and medicinal chemistry. However, catalytic asymmetric synthesis chiral are much less...

Enantioselective sulfonylation through a copper-catalyzed three-component reaction of propargylic cyclic carbonates, cyclopropan-1-ols with sulfur dioxide is reported, allowing the preparation tertiary sulfones quaternary stereocenters. This enantioselective propargylic...

Abstract A synthetically useful 1,3‐insertion reaction of a rhodium‐carbenoid into the C( sp 2 )H bond simple indole is disclosed, which produces structurally divergent 2‐indolylenamides in good to excellent yields and decent chemo‐ regioselectivities. The obtained tryptamine vinylogues can be transformed biologically important derivatives or 3,3′‐biindoles with ease. magnified image

A PtII-catalyzed intramolecular chemo- and regioselective pentannulation/long-range 1,5-acyl migration reaction is described. This cascade cycloisomerization protocol produces a wide variety of benzofulvene diketones in good to excellent yields with exclusively the Z configuration exocyclic double bond final product. The 18O isotope experiment together 13C NMR, HRMS, HMBC analyses confirmed an interesting long-range acyl rearrangement process this transformation.

Abstract A highly efficient synthesis of unsymmetrical sulfoximine ureas is developed. The reaction unites simple N H‐sulfoximines and acyl azides by a formal Curtius rearrangement as the key step. This could be easily scaled up to gram scale omits generation hazardous byproducts, thus allowing practical environmentally benign path for medicinally important sulfonimidoyl ureas.

A highly regioselective sequential 1,3-acyloxy migration/pentannulation/1,5-hydride migration reaction is disclosed which provides an efficient access to (E)-2-vinyl-3-oxo-1-methyleneindenes under neutral and mild conditions. The migrated hydrogen atom was derived from unactivated alkyl group, the long-range 1,5-H shift confirmed through related deuterium experiments.

Organophosphorus aza-heterocycles are widely found in the framework of numerous bioactive molecules, functional materials, and commercially available drugs. We report herein a photoredox-catalyzed radical addition cascade annulation sequence acyclic phosphinimides with variety organohalides under mild external oxidant-free reaction conditions. A wide range functionalized bearing quaternary carbon center could be efficiently selectively produced by employing diverse precursors, including...