Synthesis of new 8-arylisoquinoline derivatives by application of palladium-catalyzed Suzuki cross-coupling reactions

New 8-(het)aryltetrahydroisoquinolines (10-14), 8-aryltetrahydroisoquinolin-4-ols (15,16), and 8-phenylisoquinolin-4-ol (17), flexible analogues of aporphine, were synthesized in good yields using palladium-catalyzed Suzuki cross-coupling reactions from 8-bromotetrahydroisoquinolin-4-one (6) as a common intermediate. We also describe the synthesis of this novel intermediate through an easy and efficient method, which involved intramolecular Friedel-Crafts cyclization.     

High-Resolution X-ray Study of the Smectic A-Smectic B Phase Transition and the Smectic B Phase in Butyloxybenzylidene Octylaniline

We have carried out a high resolution X-ray study of the smectic phases of Butyloxybenzylidene Octylaniline. We find that the phase previously identified as Smectic-B in this material is crystalline with in-plane order extending over at least 1.4 μm. The in-plane Bragg peaks are accompanied by anomalously strong diffuse scattering that can be described by a form 1/(q ²⊥ + γ² q ² _z). Unless the elastic constant C₄₄ is more than an order of magnitude smaller than previously reported values of ～ 10⁸ ergs/cm³ the diffuse scattering can not be due to acoustic phonons. The crystalline-B to Smectic-A melting transition is strongly first order with no observable pre-transition effects on either side of the transition.     

PEPPSI-Pd-NHC catalyzed Suzuki-Miyaura cross-coupling reactions in aqueous media

A series of unsymmetrical 1,3-disubstituted benzimidazolium chlorides were synthesized as N-heterocyclic carbene (NHC) precursors. These compounds were used to synthesize of the PEPPSI-type palladium NHC complexes. The structures of all compounds were characterized by ¹H NMR, ¹³C NMR, FT-IR spectroscopy and elemental analyses. The catalytic activity of the PEPPSI-type palladium–NHC complexes has been evaluated with respect to the Suzuki-Miyaura cross-coupling reactions of phenyl boronic acid with various aryl halides in aqueous media.     

One-pot propagation of (Hetero)Arylamines: Modular synthesis of diverse Amino-di(hetero)arylamines

Formal propagation of (hetero)arylamine is achieved via a one-pot Buchwald–Hartwig C–N cross-coupling and nitro reduction sequence, enabling a rapid modular synthesis of diverse amino-di(hetero)arylamines from (hetero)arylamines and halogenated nitrobenzenes. Various functionalized aromatic amines with different electronic and steric environments can be efficiently prolongated to formally incorporate another arylamino fragments. This approach has been successfully applied in the synthesis of more than forty amino-di(hetero)arylamines. The applicability of this method has also been demonstrated in the synthesis of oligoanilines and the tyrosine-kinase inhibitor Imatinib.     

Mechanistic Dichotomy of Magnesium‐ and Zinc‐Based Germanium Nucleophiles in the C(sp3)−Ge Cross‐Coupling with Alkyl Electrophiles

Robust procedures for two mechanistically distinct C(sp³)?Ge bond formations from alkyl electrophiles and germanium nucleophiles are reported. The germanium reagents were made available as bench‐stable solutions by lithium‐to‐magnesium and lithium‐to‐zinc transmetalation, respectively. The germanium Grignard reagent reacts with various primary and secondary alkyl electrophiles by an ionic nucleophilic displacement. Conversely, the coupling of the corresponding zinc reagent requires a nickel catalyst, which then engages in radical bond formations with primary, secondary, and even tertiary alkyl bromides. Both methods avoid the regioselectivity issue of alkene hydrogermylation and enable the synthesis of a wide range of functionalized alkyl‐substituted germanes.     

Late‐Stage Functionalization of Peptides and Cyclopeptides Using Organozinc Reagents

We report a new late‐stage functionalization of small peptides and cyclopeptides relying on the Negishi cross‐coupling of readily prepared iodotyrosine‐ or iodophenylalanine‐containing peptides with aryl‐, heteroaryl‐, and alkylzinc pivalates or halides. In silico and in vitro determinations of membrane permeability parameters of the modified cyclopeptides showed that in most cases, the solubility was improved by the introduction of polar pyridyl units while the cell‐membrane permeability was maintained.     

Palladium‐Catalyzed Electrophilic Functionalization of Pyridine Derivatives through Phosphonium Salts

Herein, we report a highly efficient and practical method for pyridine‐derived heterobiaryl synthesis through palladium‐catalyzed electrophilic functionalization of easily available pyridine‐derived quaternary phosphonium salts. The nice generality of this reaction was goes beyond arylation, enabling facile incorporation of diverse carbon‐based fragments, including alkenyl, alkynyl, and also allyl fragments, onto the pyridine core. Notably, the silver salt additive is revealed to be of vital importance for the success of this transformation and its pivotal role as transmetallation mediator, which guarantees a smooth transfer of pyridyl group to palladium intermediate, is also described.     

Preparation of aryl azides of aryl boronic acids and one-pot synthesis of 1,4-diaryl-1,2,3-triazoles by a magnetic cysteine functionalized GO–CuI/II nanocomposite

A mixed Cu^I/Cu^IIcatalyst based on magnetic cysteine functionalized graphene oxide (Cu^I/II@Cys-MGO) was prepared and used for the azidonation reaction of aryl boronic acids and one-pot synthesis of 1,4-diaryl −1,2,3-triazoles. Aryl azides were obtained in good yields and short reaction times via cross-coupling of aryl boronic acids with sodium azide in the presence of Cu^II catalytic species in this catalytic system. The azide-alkyne cycloaddition reaction was catalyzed by CuI catalytic species in Cu^I/^II@Cys-MGO nanocomposite.     

Ligand-Enabled Nickel-Catalyzed Redox-Relay Migratory Hydroarylation of Alkenes with Arylborons

A redox-relay migratory hydroarylation of isomeric mixtures of olefins with arylboronic acids catalyzed by nickel complexes bearing diamine ligands is described. A range of structurally diverse 1,1-diarylalkanes, including those containing a 1,1-diarylated quaternary carbon, were obtained in excellent yields and with high regioselectivity. Preliminary experimental evidence supports the proposed non-dissociated chainwalking of aryl-nickel(II)-hydride species along the alkyl chain of alkenes before selective reductive elimination at a benzylic position. A catalyst loading as low as 0.5 mol % proved to be sufficient in large-scale synthesis while retaining high reactivity, highlighting the practical value of this transformation.