Several bidentate dihydroimidazolines were prepared and investigated as catalysts for hydrogen transfer reduction of C═N bond with Hantzsch ester. Highly efficient reactions observed quinolines imines low catalyst loading 2 mol %. The presence halogen bonding was elucidated using NMR studies isothermal calorimeric titrations. Binding constants the XB donors also measured titrations (ITC).

Herein we report the conjugate borylation of vinyl sulfones mediated by ion pairing, which enables efficient synthesis β-sulfonyl alcohols bearing diverse functionalities in 13–98% yields. Further mechanistic investigations...

Highly enantioselective allylic alkynylation of racemic bromides under biphasic condition is furnished in this report. This approach employs functionalized terminal alkynes as pro-nucleophiles and provides 6- 7-membered cyclic 1,4-enynes with high yields excellent enantioselectivities (up to 96% ee) mild conditions. Enantioretentive derivatizations highlight the synthetic utility transformation. Cold-spray ionization mass spectrometry (CSI-MS) X-ray crystallography were used identify some...

Abstract An enantioconvergent synthesis of chiral cyclic allylboronates from racemic allylic bromides was achieved by using a guanidine–copper catalyst. The were obtained with high γ/α regioselectivities (up to 99:1) and enantioselectivities 99 % ee ), could be further transformed into diverse functionalized compounds without erosion optical purity. Experimental DFT mechanistic studies support an S N 2′ borylation process catalyzed monodentate guanidine–copper(I) complex that proceeds...

Regioselective C-H functionalization of pyridines remains a persistent challenge due to their inherent electronically deficient properties. In this report, we present strategy for the selective pyridine C3-H thiolation, selenylation, and fluorination under mild conditions via classic N-2,4-dinitrophenyl Zincke imine intermediates. Radical inhibition trapping experiments, as well DFT theoretical calculations, indicated that thiolation selenylation proceeds through radical addition-elimination...

An efficient, general, one-pot, three-component procedure for the preparation of 3,5-disubstituted 1<i>H</i>-pyrazoles via condensation substituted aromatic aldehydes, tosylhydrazine and terminal alkynes in toluene is reported. The reaction tolerates a variety functional groups sterically hindered substrates to afford desired pyrazoles yields 67–91%.

Abstract Herein, we report the conjugate addition of α,β‐unsaturated carbonyl compounds to thiophene derivatives. We used a 2‐iodoimidazolinium triflate salt as halogen‐bonding donor, which afforded moderate‐to‐excellent yields corresponding alkylated thiophenes. Insight into catalytic process was obtained from 1 H NMR spectroscopy studies and DFT calculations, indicated halogen‐bonding‐supported mechanism with limited Brønsted acid catalysis.

An efficient method has been developed for Michael/Electrophilic substitution cascade reaction between 3‐pyrrolyl‐oxindoles and unsaturated ketoesters, utilizing bifunctional organocatalysis. This approach enables the synthesis of a diverse array spiro‐oxindole derivatives bearing three stereogenic centers, two them quaternary, achieving high yields exceptional diastereoselectivities. Furthermore, resulting products can be readily converted into tetrahydropyridine skeletons through an...

Abstract An efficient addition‐oxidation cascade reaction has been developed between α‐ aminomaleimide and vinylogous oxindole with strong electron‐withdrawing group (‐CN or ‐COCOOR), enabling the synthesis of a diverse array tetrasubstituted olefins high yields exceptional diastereoselectivities (up to 98% yield up &gt;20:1 Z / E ). The tolerance free amine investigated, results demonstrated that most could not affect nucleophilic addition step except for aliphatic primary amines....

Abstract Multiple block copolymers bearing PDMAEMA (poly(2‐(dimethylamino)ethyl methacrylate), PLMA (poly(lauryl and PAMA (poly(allyl methacrylate) segments are synthesized via RAFT (reversible addition‐fragmentation chain transfer) polymerization. Manipulating the cross‐linkage of in specific domain polymeric assemblies affords micellar nanoreactors with different topological structures. After embedded Pd NPs (nanoparticles) corona layer, core‐cross‐linked micelles demonstrate profound...

Herein copper-catalyzed Markovnikov protoborylation of unactivated terminal alkenes was achieved through the employment a bulky σ-donating guanidine ligand. The reaction demonstrated good tolerance to diverse functional groups and remarkable selectivity for branched borylation products (86:14-97:3) under ambient conditions, which enabled synthesis secondary alkyl boronates in grams with further valuable derivatizations. Mechanistic studies suggested boryl insertion C═C bonds via Cu-guanidine...

Novel degradable and chemically recyclable polymers were synthesized using five-membered cyclic ketene hemiacetal ester (CKHE) monomers.

A one-pot cascade reaction for 2,3-dihydropyridinone synthesis was accomplished with 3-fluoro-2-iodo-1-methylpyridinium triflate as the halogen bond catalyst. The desired [4+2] cycloaddition products, bearing aryl, heteroaryl, alkyl, and alicyclic substituents, were successfully furnished in 28-99% yields. Mechanistic investigations proved that a strong halogen-bonding interaction forged between iodopyridinium catalyst imine intermediate essential to dynamically masking vulnerable C-I on...

Visible-light photoredox catalysis plays an important role in various reactions which are inaccessible under typical thermal conditions. Distinctly different from common visible-light often involves transition-metal complexes, conjugated organic dyes, or electron donor–acceptor herein, the use of ion-pair charge-transfer (IPCT) complex-induced catalytic described, wherein cyclization–methoxylation N-vinyl amides methanol was achieved irradiation with blue LEDs. The reaction employs a...

The catalyst-free oxidative cleavage of (<italic>Z</italic>)-triaryl-substituted alkenes bearing a pyridyl motif in ambient air under the irradiation blue LEDs has been developed.

Recently, we realized the highly selective one-pot synthesis of 2,6-diarylpyridines by using a Pd-catalyzed direct C-H arylation approach via transient activator strategy. Although methylation reagent as and Cu(I) salt or oxide were found to be prerequisites, details regarding mechanism remained unclear. In this paper, DFT calculations combined with experimental investigations carried out elucidate principle features transformation. The results reveal (1) origin exquisite diarylating...

Abstract An enantioconvergent synthesis of chiral cyclic allylboronates from racemic allylic bromides was achieved by using a guanidine–copper catalyst. The were obtained with high γ/α regioselectivities (up to 99:1) and enantioselectivities 99 % ee ), could be further transformed into diverse functionalized compounds without erosion optical purity. Experimental DFT mechanistic studies support an S N 2′ borylation process catalyzed monodentate guanidine–copper(I) complex that proceeds...

Merging the stereoisomeric mixture of substrate into a single product through stereospecific transformation is challenging but higher‐order synthetic strategy, which perfectly meets demand cost control in precise chemical production. In this work, stereoconvergent synthesis Z‐allylic boronates was realized with protoborylation E/Z‐mixed 1,3‐dienes catalyzed by novel copper‐guanidine complex. The reaction could proceed smoothly under very mild conditions good functional group tolerance, and...

Abstract ABC‐type miktoarm star copolymers are synthesized using a single living radical polymerization (organocatalyzed polymerization) via “combinatorial” approach. The arm A is poly(butyl acrylate), the B poly(methyl methacrylate), and C encompasses hydrophobic hydrophilic polyacrylates. acrylate) with vinyl chain end (macromonomer) synthesized. methacrylate) subsequently connected to reactive group generate diblock copolymer. From junction of copolymer, polymer grew yield copolymers. An...

Abstract A direct C−H phosphonylation of pyridine by N ‐benzylating activation is reported, which afforded 4‐pyridylphosphine oxides with high regioselectivity, without the employment metal catalyst or expensive activator. By increasing electrophilicity pyridinium electron‐withdrawing substituents on ‐benzyl group, process could be realized at room temperature. Control experiments and NMR investigation confirmed interaction between DBU diphenylphosphine oxide generated true phosphorus...

A facile and novel approach for the highly chemo- stereoselective synthesis of ( Z )-β-iodoenamides from N -vinyl amides has been developed based on a visible-light-induced ion pair charge transfer state derived pyridinium iodides.