A rhodium-catalyzed tandem enantioselective C–H silylation/alkene hydrosilylation of dihydrosilanes, which enables the streamlined construction a wide range silicon-stereogenic silanes, is successfully developed. This process involves SiH2-steered highly silylation to furnish corresponding desymmetric monohydrosilanes, are subsequently trapped with alkenes in stereospecific fashion build functionally diverse asymmetrically tetrasubstituted silanes. general strategy combines readily available...

Abstract A rhodium(I)‐catalyzed enantioselective silylation of aliphatic C−H bonds for the synthesis silicon‐stereogenic dihydrobenzosiloles is demonstrated. This reaction involves a highly intramolecular C(sp 3 )−H dihydrosilanes, followed by stereospecific intermolecular alkene hydrosilylation leading to asymmetrically tetrasubstituted silanes. wide range dihydrosilanes and alkenes displaying various functional groups are compatible with this process, giving access variety functionalized...

Catalytic enantioselective intermolecular C-H silylation offers an efficient approach for the rapid construction of chiral organosilicon compounds, but remains a significant challenge. Herein, new type silyl ligand is developed, which enables first iridium-catalyzed atroposelective reaction 2-arylisoquinolines. This protocol features mild conditions, high atom economy, and remarkable yield with excellent stereoselectivity (up to 99 % yield, ee), delivering enantioenriched axially silane...

The reductive cleavage of C(Ar)-X bonds is the key step for cross coupling Ar-X with other groups. In this work, under irradiation 407 nm LEDs using sodium formate as reductant and thiol hydrogen atom transfer agent, a variety (hetero)aryl chlorides, bromides, iodides could be reduced to corresponding (hetero)arenes. intermediates, aryl radicals, trapped by either hydrogen, phosphite, or borates. same reduction conditions can extended deprotection sulfonamides.

The reaction of quaternary ammonium salts <italic>via</italic> C–N bond cleavage to construct C–C, C–H and C–heteroatom bonds is summarized.

Abstract C- 1 Glycals serve as pivotal intermediates in synthesizing diverse C -glycosyl compounds and natural products, necessitating the development of concise, efficient user-friendly methods to obtain glycosides is essential. The Suzuki-Miyaura cross-coupling glycal boronates notable for its reliability non-toxic nature, but donor stability remains a challenge. Herein, we achieve significant breakthrough by developing stable boronates, effectively overcoming issue glycal-based...

Metabolically robust C‐glycosides are crucial in various biological and medical applications, underscoring the need for efficient synthesis methods. While radical C‐glycosylation reactions known their reliability functional group tolerance, challenges such as glycosyl donor stability atom economy persist. In this study, we investigate underexplored potential of condition‐controlled divergent through a switchable photocatalytic strategy, involving reductive anomeric C–O bond cleavage....

Metabolically robust C‐glycosides are crucial in various biological and medical applications, underscoring the need for efficient synthesis methods. While radical C‐glycosylation reactions known their reliability functional group tolerance, challenges such as glycosyl donor stability atom economy persist. In this study, we investigate underexplored potential of condition‐controlled divergent through a switchable photocatalytic strategy, involving reductive anomeric C–O bond cleavage....

Nickel-catalyzed cross-coupling of allyl alcohols with aryl- and alkenylzinc chlorides through C-O bond cleavage was performed. Reaction (E)-3-phenylprop-2-en-1-ol 1-aryl-prop-2-en-1-ols or gave linear products. 1-phenyl- 1-methyl-substituted resulted in 3-aryl/alkenyl-substituted (E)-(prop-1-ene-1,3-diyl)dibenzenes (E)-(but-1-enyl)benzene. alcohol p-Me2NC6H4ZnCl a mixture normal coupling product 4-allyl-N,N-dimethylaniline its isomerized N,N-dimethyl-4-(prop-1-en-1-yl)aniline.

A methodology that allows for the construction of C-P bonds via nickel-catalyzed cross-coupling organoammonium salts with appropriate phosphorus nucleophiles has been developed. Aryl-, pyridyl-, benzyl-, and allyl-ammonium triflates can be employed as electrophiles. The phosphorus-based included diaryl/dibutyl phosphine oxide, dialkyl phosphonates, ethyl phenylphosphinate. Functional groups OMe, CN, CF3, F, Cl, C(O)NMe2, C(O) tBu were tolerated.

Abstract Base-promoted C-H cleavage without transition metals opens a practical alternative for the one based on noble or radical initiators. The resulting carbanion can pass through addition to unsaturated bonds like C-N C-C triple bonds, in which stoichiometric oxidants are needed. When situ meets catalytic carbanion-radical relay, it turns be challenging but has not been accomplished yet. Here we report combination of base-promoted benzylic and copper-catalyzed redox relay. Catalytic...

The first example of phenanthroline-tBuOK promoted intramolecular radical C–H arylation N-(2-iodobenzyl)indoles without involvement transition metals has been developed. A variety substituted 6H-isoindolo [2, 1-a] indoles were prepared by a simple and efficient cyclization using 1,10-phenanthroline in the presence potassium tert-butoxide chlorobenzene. This strategy provides fast versatile access to isoindolo[2,1-a]indole derivatives for synthesis pharmaceuticals organic electroluminescent...

We herein report an efficient one-pot strategy for the stereodivergent asymmetric synthesis of various P-atropisomeric Si-stereogenic monohydrosilanes with excellent stereoselectivity from dichlorosilanes.

Nonclassical C-glycosides, distinguished by their unique glycosidic bond connection mode, represent a promising avenue for the development of carbohydrate-based drugs. However, accessibility nonclassical C-glycosides hinders broader investigations into structural features and modes action. Herein, we present first example Pd-catalyzed stereospecific glycosylation anomeric stannanes with aryl or vinyl halides. This method furnishes desired in good to excellent yields, while allowing exclusive...

Synthetically useful 4-acetonylindoles have been conveniently prepared from 2-alkynylanilines and silyl enol ethers using a dearomatization strategy. The two-step/one-pot protocol involves an iodosylbenzene-mediated oxidative silver-catalyzed domino reaction.

The P,N,N-pincer nickel complex [Ni(Cl){N(2-Ph2PC6H4)(2′-Me2NC6H4)}]-catalyzed allyl-aryl coupling was studied. reaction of allyl methyl ethers, including (1-methoxyallyl)arenes and (3-methoxyprop-1-en-1-yl)arenes, with arylzinc chlorides afforded linear (E)-alkenes in high yields, whereas the (E)-1-methoxytridec-2-ene p-Me2NC6H4ZnCl generated a mixture branched alkenes.

NiCl2(PMe3)2-catalyzed reaction of allyl alcohols with silylzinc reagents, including PhMe2SiZnCl, Ph2MeSiZnCl, and Ph3SiZnCl, was performed, achieving allylsilanes in high yields. Aryl- heteroaryl-substituted alcohols, (E)-3-arylprop-2-en-1-ols, 1-aryl-prop-2-en-1-ols, (E)-1-phenylpent-1-en-3-ol can be employed the transformation. A range functional groups as well heteroaryl were tolerated. Reaction exhibited regioselectivity E/Z-selectivity when 1- or 3-aryl-substituted used substrates....

By choosing different phosphine ligands, nickel-catalyzed selective alkylation and reduction of allylic alcohols with alkyl Grignard reagents were performed. The reaction using Ni(dppe)Cl2 as the catalyst resulted in cross-coupling primary cyclopropylmagnesium bromide. catalyzed by combination Ni(PCy3)2Cl2 dcype led to alcohols. Secondary except bromide always either or Ni(PCy3)2Cl2/dcype catalyst. In reductive β-H-containing required.

Abstract A rhodium(I)‐catalyzed enantioselective silylation of aliphatic C−H bonds for the synthesis silicon‐stereogenic dihydrobenzosiloles is demonstrated. This reaction involves a highly intramolecular C(sp 3 )−H dihydrosilanes, followed by stereospecific intermolecular alkene hydrosilylation leading to asymmetrically tetrasubstituted silanes. wide range dihydrosilanes and alkenes displaying various functional groups are compatible with this process, giving access variety functionalized...

In this work, CuSO4 is utilized as a practical redox catalyst for tandem dual annulation in the synthesis of indole-fused tetracyclic heteroacenes, which are important skeletons both medicinal chemistry and materials chemistry. The preparation such convenient efficient manner high demand. This method realizes modular benzofuro-, benzothieno-, indoloindoles from abundant feedstocks 2-halobenzyl halides nitrile derivatives up to 99% yields, providing rapid access diverse heteroacenes with...

Abstract A series of cis ‐restricted 4,5‐diaryl‐3‐aminopyrazole derivatives were synthesized and tested for their cytotoxic activity in vitr o against five human cancer cell lines (K562, ECA‐109, A549, SMMC‐7721, PC‐3). Compounds 5a , 5b 5d 6b showed potent cytotoxicity all lines. Primary mechanism research on compound indicated that it was a inhibitor tubulin polymerization, arresting cycle G 2 /M phase. The docking the conformation overlaps well with CA‐4 crystallized protein complex,...

Abstract Catalytic enantioselective intermolecular C−H silylation offers an efficient approach for the rapid construction of chiral organosilicon compounds, but remains a significant challenge. Herein, new type silyl ligand is developed, which enables first iridium‐catalyzed atroposelective reaction 2‐arylisoquinolines. This protocol features mild conditions, high atom economy, and remarkable yield with excellent stereoselectivity (up to 99 % yield, ee ), delivering enantioenriched axially...