Cu-catalyzed synthesis of 3-etherified azaspiro[4.5]trienones from N-arylpropiolamides and ethers is presented using TBHP oxidant. This achieved through C(sp3)–H functionalization, ipso-carbocyclization dearomatization, this method represents a new example alkyne oxidative 1,2-difunctionalization with an ipso-aromatic carbon bond by simultaneously forming two carbon–carbon bonds.

A novel metal-free oxidative 1,2-alkylarylation of unactivated alkenes with the α-C(sp(3))-H bonds acetonitriles for synthesis 5-oxo-pentanenitriles is presented. In presence TBPB (tert-butyl peroxybenzoate), a variety α-aryl allylic alcohols underwent reaction acetonitriles, giving in good to excellent yields. This method proceeds via C(sp(3))-H coupling C-C double bond and 1,2-aryl-migration, represents new access acyclic molecules through alkene 1,2-alkylarylation.

The functionalization of unactivated C(sp3)─H bonds represents one the most powerful and atom-economical tools for formation new carbon-based chemical in synthesis. Although cross-dehydrogenative coupling reactions two distinct C─H carbon-carbon have been well investigated, controlled functionalizations or more different across a functional group molecule (e.g., an alkene alkyne) single reaction remain challenging. Here, we present three-component dialkylation alkenes with common alkanes...

A copper-catalyzed remote benzylic C-H functionalization strategy enabling 1,2-difunctionalization of alkenes with 2-methylbenzeneamides and nucleophiles, including alcohols, indoles, pyrroles, the intrinsic amino groups, is reported, which characterized by its redox-neutral conditions, exquisite site-selectivity, broad substrate scope, wide utilizations late-stage modifying bioactive molecules. This reaction proceeds through nitrogen-centered radical generation, hydrogen atom transfer,...

A new metal-free oxidative decarbonylative [2 + 2 2] carbocyclization of<italic>N</italic>-(2-ethynylaryl)acrylamides with tertiary and secondary alkyl aldehydes is described.

The first aryl carboxyl radical generation by the donor–acceptor complex with N-acyloxyphthalimides and Hantzsch esters is reported. Regio- chemoselective C(sp3)–H bond allylation enabled radicals visible light irradiation under mild metal-free conditions.

For straightforward access to various substituted 1,1-diarylalkanes a photoredox-catalyzed and copper-promoted 1,2-alkylarylation reaction of styrenes has been developed, which uses α-carbonyl alkyl bromides N,N-disubstituted anilines as functionalization reagents. In this radical difunctionalization reaction, bromides, including primary-, secondary- tertiary-α-bromoalkyl ketone esters, malonic esters cycloalkane were transformed the corresponding in moderate good yields at room temperature....

A new, three-component 1,2-alkylamination of styrenes with alkyl N-hydroxyphthalimide (NHP) esters and amines by Lewis acid visible-light photoredox cooperative catalysis is described. This reaction employs NHP as general alkylation reagents to accomplish the alkenes in high efficiency excellent functional groups tolerance, significantly enhancing synthetic potential 1,2-alkylaminations for accessing complex functionalized amines.

Abstract A new visible light‐initiated 1,5‐hydride radical shift strategy has been developed to enable the one‐step functionalization of both a C( sp 3 )Br bond and )H adjacent same carbon atom. This light photoredox catalysis offers mild straightforward access diverse five‐membered carbocyclic ring‐fused polycyclic hydrocarbons with high turnover numbers (TONs; up 4.93×10 ) broad substrate scope. magnified image

A silver-catalyzed oxidative intermolecular [3 + 2]/[5 2] annulation of N-arylpropiolamides with 4-vinyl acids for producing fused 2H-benzo[b]azepin-2-ones is described. This radical-mediated reaction features broad substrate scope and excellent selectivity, enables the formation three new C–C bonds through decarboxylation, annulations, C(sp2)-H functionalization cascades. Employing this strategy, common terminal alkynes were successfully converted into cyclopentenes via annulation.

A visible-light-induced alkene difunctionalization strategy is described for 1,5-dicarbonyl compound synthesis through alkylation and 1,2-aryl migration.

Oxidative radical cleavage of Si–H/silyl C(sp³)–H bonds, dual Si–H bonds and Si–H/Si–Si toward Si-heterocycles is presented.

A general, ideal atom utilization electrochemical technology to enable alkene alkoxyhalogenation and organohalide dehalogenation in one pot is presented. This highlighted by convergent strategy integrating several reactions, such as alkoxyhalogenation, dehalogenation, deuteration. Experimental data suggest that alkenes have the lowest oxidation potential, which lead anodic conversion of C═C bond radical cation intermediates, cathodic transformations organohalides, including alkyl aryl...

A cooperative nickel and photoredox reductive catalysis for 1,4-dicarbofunctionalization of 1,3-enynes with tertiary N-methylamines organohalides to produce tetrasubstituted allenes is presented. This method enables the generation aminoalkyl C(sp3)-centered radicals by site selective cleavage N-methyl C(sp3)–H bonds in extended alkyl bromides as electrophilic terminating regents. Mechanistic studies indicate that reaction involves a radical process Ni0/NiI/NiIII catalytic cycle.

A conceptually novel single electron transfer strategy for C(sp3)–F activation-enabled [3 + 2 1] annulation of α-polyfluoromethyl alkenes is developed.

A selectivity-control approach for palladium-catalyzed dearomative para-/ortho-cycloaddition cascades of aromatic compounds with 1,4-enynes and CO via a skeletal reorganization process to produce polycycle-fused bicyclo[2.2.2]octenes is reported. This mechanistically novel depends on that consists sequence [4 + 2] para-cycloaddition, 3,3-Cope rearrangement, carbon–carbon bond activation/[4 cycloaddition.

A general and atom-economical electrochemical dehydrogenative method for the intermolecular 1,2-alkylarylation of styrenes with malonates nucleophilic N-heteroarenes (including indoles pyrroles) has been developed. This transformation provides a regioselective route to construct highly valuable 1,1-diarylalkanes enabled by C(sp3)-H/C(sp2)-H functionalization under mild conditions, H2 is only theoretical byproduct. Mechanistic studies indicated that reaction proceeded through oxidative...

Abstract We study the effects of gas adsorption on dynamics and stability nanobubbles at solid-liquid interface. The phase diagram dynamic evolution surface were analyzed under varying equilibrium constant. Four distinct behaviors appear in diagram: shrinking to dissolution, expanding bursting, stability, stability. Special boundary states are identified diagram, where continuous growth can take place even very weak gas-surface interaction or with small initial bubble size. Surface plays a...

An efficient and highly convergent total synthesis of the potent antitumor agent phorboxazole B has been achieved. The synthetic strategy this features: 1) a substrate-controlled hydrogenation to construct functionalized cis-tetrahydropyrane unit; 2) iterative crotyl addition synthesize segment that contains alternating hydroxyl methyl substituents; 3) Hg(OAc)2/I2-induced cyclization establish moiety; 4) 1,3-asymmetric induction in Mukaiyama aldol reaction afford stereogenic centers at C9...

Traditional micelle self-assembly is driven by the association of hydrophobic segments amphiphilic molecules forming distinctive core-shell nanostructures in water. Here we report a surprising chaotropic-anion-induced micellization cationic ammonium-containing block copolymers. The resulting nanoparticle consists large number ion pairs (≈60,000) each core. Unlike chaotropic anions (e.g. ClO4(-)), kosmotropic SO4(2-)) were not able to induce formation. A positive cooperativity was observed...

A new metal-free aldehyde auto-oxidation strategy that allows the decarbonylative formation of homoallyl radical capable cascade annulations with alkynes is described. By using various N-arylpropiolamides, oxidative [3 + 2]/[5 2] annulation reaction was achieved to produce benzo[b]cyclopenta[e]azepin-4(1H)-ones, which represent a powerful platform for intermolecular cycloadditions alkyne broad substrate scope and high selectivity.

A new transition-metal-free photoredox decarboxylative alkylation of α,β-unsaturated carboxylic acids and alkyl<italic>N</italic>-hydroxyphthalimide (NHP) esters by NaI/PPh₃catalysis has been developed.

A copper-catalyzed divergent annulation of N-fluoro-N-alkylsulfonamides with terminal alkynes enabled by remote C(sp3)–H functionalization for producing 2,3-dihydro-1H-pyrroles and 1,2,3,4-tetrahydropyridines is reported. Using a alkyne to capture an amidyl radical forms vinyl carbon-centered radical, which would sequentially undergo 1,5- or 1,6-hydrogen atom transfer (HAT) site-selectively enable the challenging bonds at β- γ-position nitrogen in N-fluorosulfonamides, thus resulting...

A practical and eco-friendly strategy for the radical-mediated decarboxylative [3 + 2] [4 annulation of enynals γ,σ-unsaturated N-(acyloxy)phthalimides through photoactivation an electron donor-acceptor (EDA) complex has been developed. wide range primary, secondary, tertiary alkyl N-hydroxyphthalimide (NHP) esters can be used as suitable substrates synthesis fused ketones without any transition-metal catalysts or oxidants. This protocol features a broad substrate scope, excellent...