In this review, we provide a comprehensive overview of recent progress in rapidly growing field by summarizing the 1,6-conjugate addition and annulation reactions <italic>p</italic>-QMs with consideration their mechanisms applications.

To realize the molecular design of new functional silver(I) clusters, a synthetic approach has been proposed, by which weakly coordinating ligands NO3– in Ag20 thiolate cluster precursor can be substituted carboxylic while keeping its inner core intact. By rational design, novel atom-precise or amino acid protected 20-core Ag(I)-thiolate clusters have demonstrated for first time. The fluorescence and electrochemical activity postmodified modulated alrestatin ferrocenecarboxylic substitution....

Abstract A metal‐free [2+2] cycloaddition and 1,4‐addition sequence induced by S‐centered radicals has been achieved treating benzene‐linked allene‐ynes with aryldiazonium tetrafluoroborates DABCO‐bis(sulfur dioxide) in a one‐pot procedure. The reaction provides greener more practical access to functionalized cyclobuta[a]naphthalen‐4‐ols valuable applications. More than 50 examples are demonstrated excellent diastereoselectivity chemical yields. pathway is proposed proceed the following...

Chiral metal-organic frameworks (MOFs) are usually endowed by chiral linkers and/or guests. The strategy using secondary building units in MOFs for solving the trade-off of circularly polarized luminescence (CPL)-active materials, high photoluminescence quantum yields (PLQYs) and dissymmetry factors (|glum |) has not been demonstrated. This work directionally assembles predesigned silver clusters with ACQ through reticular chemistry. nanoscale chirality cluster transmits MOF's framework,...

Abstract The development of stimuli‐responsive circularly polarized luminescence (CPL) materials is quite attractive but challenging. Here, a pair atomically precise enantiomers R/S ‐Ag 20 nanoclusters has been synthesized using chiral acid ligands. And then, CPL were developed by assembling the silver with an achiral bridging ligand. cluster‐assembled produce dissymmetry factor (| g lum |) 1 × 10 −3 , through high‐efficiency induction process. More interestingly, single band at room...

The photocatalyzed radical-triggered thio/selenosulfonylation–bicyclization of indole-tethered 1,6-enynes has been established for the first time, enabling synthesis various previously unreported thio/selenosulfonylated benzo[c]pyrrolo[1,2,3-lm]carbazoles with moderate to good yields under mild conditions. reaction pathway was proposed, consisting energy transfer, homolytic cleavage, radical addition, 5-exo-dig, coupling, and a Mallory cascade. This approach exhibits wide substrate...

Comprehensive Summary A general and convenient photoredox‐catalyzed acylation alkylcyanation of MBH acetates has been established, enabling the assembly C(sp 2 )–C(sp 3 ) bond by a nitrogen‐centered radical strategy for synthesis trisubstituted alkenes in moderate to excellent chemical yields (48 examples total). The reaction with acyl (indanone) oxime esters afforded containing 1,4‐dicarbonyl groups. Interestingly, use Eosin Y as photocatalyst catalytic system resulted formation distal...

Comprehensive Summary Yne‐allenes bearing both a C—C triple bond and an allene unit are class of focal substrates in organic synthesis, view their structure diversity, high reactivity intermediate variety the past years. Engaging yne‐allenes numerous annulation cascades provides efficient direct accesses to elaborate functionalized polycyclic molecular architectures convergent manner. There lots types catalytic chemical reactions such as intramolecular cyclizations, cycloisomerizations,...

The Cu(I)-catalyzed annulation-halotrifluoromethylation and cyanotrifluoromethylation of enynones have been established, enabling multibond formations the synthesis quaternary carbon-centered 1-indanones in moderate to good chemical yields. reaction with Togni's reagent chloro- or bromotrimethylsilane afforded halo- CF3-containing 1-indenones. However, addition K3PO4 as a base into catalytic system led forming cyano-anchored (Z)-1-indanones major stereoisomeric products. This strategy...

A series of new targets containing 3 chiral elements central, orientational, and turbo chirality have been designed synthesized asymmetrically. The absolute configurations conformations these types were concurrently controlled by using sulfonimine auxiliary unambiguously determined x-ray diffraction analysis. These include alpha unnatural amino acid derivatives, which may play an important role for drug design, discovery, development. Three propellers framework are covalently connected to a C(sp

A novel silver-chalcogenolate cluster-based framework Ag12TPPA·AA with long-lived afterglow was successfully synthesized. It transformed into more densely packed Ag12TPPA·AB and Ag12TPPA·ABC by layer sliding accompanied macroscopic crystal contraction changing luminescence.

Silver chalcogenolate clusters (SCCs) and silver cluster-assembled materials (SCAMs) are an important category of novel luminescent materials, the emission which can be modulated by variation cluster nodes linker species. Here, successfully synthesis two isostructural 2D SCAMs is reported: Ag12 bpa bpe formed using linkers with different conformational freedom (bpa=1,2-bis(4-pyridyl)ethane, bpe=1,2-bis(4-pyridyl)ethylene), dodenuclear as secondary building units (SBUs). Interestingly,...

Comprehensive Summary Developing reactions for the synthesis of 6‐6‐4 and 6‐4 carbocyclic scaffolds with a chiral quaternary center at bridgehead position is highly desired, considering existence such skeletons in natural products biological activities potential using these molecules downstream studies chemical biology medicinal chemistry. Report here accessing target high chemo‐, regio‐ enantio‐selectivities through Pd(II)/chiral N , ’‐disulfonyl bisimidazoline (Bim) ligand‐catalyzed...

General and convenient visible-light-promoted alkylsulfonylation cyanoalkylsulfonylation of MBH adducts have been developed through the multicomponent insertion sulfur dioxide, enabling assembly two C–S bonds to generate structurally diverse allylic alkylsulfones (43 examples in total). The reaction with potassium alkyltrifluoroborates 1,4-diazabicyclo[2.2.2]octane bis(sulfur dioxide) adduct afforded sulfones generally good yields. Notably, addition N,N,N′,N′-tetramethylethylenediamine as a...

Developing highly luminescent and extensively stable silver cluster-assembled materials (SCAMs) from the inferior luminogens unstable cluster is an important challenging issue. Herein, a new three-dimensional SCAM (Ag12 CPPP, [Ag12 (StBu)6 (CF3 COO)6 (CPPP)2 (DMAc)12 ]n ; CPPP=2,5-bis(4-cyanophenyl)-1,4-bis(4-(pyridine-4-yl)-phenyl)-1,4-dihydropyrrolo[3,2-b]pyrrole, DMAc=dimethylacetamide) was designed synthesized with quadridentate rigid emission ligand (CPPP) silver-chalcogenolate (SCC)...

The first thiazolium salt-catalyzed C–C triple bond cleavage of benzene-linked allene-ynes has been established.

Novel carbon–carbon triple bond breaking and rearranging reactions of benzene-linked allene–ynes have been established. The can be selectively controlled toward the formation two families skeletally diverse benzo[g]indoles 1-naphthols under mild conditions. Silver salt was found to efficiently promote indole annulation give multifunctional with installation sulfonyl groups into ring via N–S N–F cleavage NFSI, whereas NBS NCS-mediated benzannulations occurred dihalogenated 1-naphthols.

Summary of main observation and conclusion Silver cluster‐assembled materials (SCAMs) are emerging multi‐functional have attracted great attention recently. In this work, we prepared a new SCAM {[Ag 18 (S t Bu) 10 (CF 3 COO) 2 (PhPO )(PhPO H) 4 (bpy‐NH ) ]∙(PhPO H )} n (denoted as Ag bpy‐NH ), by facile one‐pot method. adopts chain‐like structure made clusters bridged bipyridyl linkers. exhibits reversible luminescent mechanochromism upon mechanical stimulation solvent treatment. Moreover,...

A novel stable 3-electron nanocluster <bold>Ag</bold>₃₄ was assembled for the first time by oxidation of a thiol, central Ag atom which replaced with Au atom, forming another alloyed <bold>Ag</bold>₃₃<bold>Au</bold>, causing change in optical absorbance and electrochemical energy gap.

So far, there have been 4 methods to control chirality including the use of chiral auxiliaries, reagents, solvents, and catalysts documented in literature textbooks. Among them, asymmetric are normally divided into homogeneous heterogeneous catalysis. In this report, we present a new type control—asymmetric catalysis via aggregates that would not belong above categories. This strategy is represented by catalytic dihydroxylation reaction olefins which ligands aggregated taking advantage...