Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Synthesis of Functionalized Azepines via Cu(I)-Catalyzed Tandem Amination/Cyclization Reaction of Fluorinated Allenynes.

ABSTRACT: An efficient method for the selective preparation of trifluoromethyl-substituted azepin-2-carboxylates and their phosphorous analogues has been developed via Cu(I)-catalyzed tandem amination/cyclization reaction of functionalized allenynes with primary and secondary amines.

SUBMITTER: Philippova AN

PROVIDER: S-EPMC9416787 | biostudies-literature | 2022 Aug

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Synthesis of Functionalized Azepines via Cu(I)-Catalyzed Tandem Amination/Cyclization Reaction of Fluorinated Allenynes.

Philippova Anna N AN Vorobyeva Daria V DV Gribanov Pavel S PS Godovikov Ivan A IA Osipov Sergey N SN

Molecules (Basel, Switzerland) 20220815 16

An efficient method for the selective preparation of trifluoromethyl-substituted azepin-2-carboxylates and their phosphorous analogues has been developed via Cu(I)-catalyzed tandem amination/cyclization reaction of functionalized allenynes with primary and secondary amines. ...[more]

PMID: 36014436

Similar Datasets

Asymmetric synthesis of dibenzo[<i>b</i>,<i>d</i>]azepines by Cu-catalyzed reductive or borylative cyclization.

Project description:A copper-catalyzed asymmetric intramolecular reductive cyclization for the synthesis of dibenzo[b,d]azepines is described. Use of 2'-vinyl-biaryl-2-imines as substrates and in situ formed [CuI/(Ph-BPE)] as the catalyst enables the synthesis of 7-membered bridged biarylamines containing both central and axial stereogenic elements in high yields (up to 98%) and with excellent diastereo- and enantioselectivities (>20 : 1 d.r., up to 99% ee). Moreover, the same catalyst was found to facilitate a related borylative cyclization to afford versatile boronic ester derivatives. Both reactions proceed under mild conditions (rt) and are applicable to a variety of substituted aromatic and heterocyclic derivatives.

| S-EPMC8635211 | biostudies-literature

Synthesis of indolines via a domino Cu-catalyzed amidation/cyclization reaction.

Project description:A highly efficient one-pot procedure for the synthesis of indolines and their homologues based on a domino Cu-catalyzed amidation/nucleophilic substitution reaction has been developed. Substituted 2-iodophenethyl mesylates and related compounds afforded the corresponding products in excellent yields. No erosion of optical purity was observed when transforming enantiomerically pure mesylates under the reaction conditions.

| S-EPMC2489202 | biostudies-literature

Pd-catalyzed stereoselective tandem ring-opening amination/cyclization of vinyl γ-lactones: access to caprolactam diversity.

Project description:A stereoselective amination/cyclization cascade process has been developed that allows for the preparation of a series of unsaturated and substituted caprolactam derivatives in good yields. This conceptually novel protocol takes advantage of the easy access and modular character of vinyl γ-lactones that can be prepared from simple precursors. Activation of the lactone substrate in the presence of a suitable Pd precursor and newly developed phosphoramidite ligand offers a stereocontrolled ring-opening/allylic amination manifold under ambient conditions. The intermediate (E)-configured ε-amino acid can be cyclized using a suitable dehydrating agent in an efficient one-pot, two-step sequence. This overall highly chemo-, stereo- and regio-selective transformation streamlines the production of a wide variety of modifiable and valuable caprolactam building blocks in an operationally attractive way.

| S-EPMC8163440 | biostudies-literature

Regioselective access to polycyclic N-heterocycles via homogeneous copper-catalyzed cascade cyclization of allenynes.

Project description:Polycyclic N-heterocycles are important structural motifs commonly found in bioactive compounds, however, their selective construction via the cyclization of allenynes remains challenging yet highly desirable. Here we show a homogeneous copper-catalyzed hetero Diels-Alder (HDA) reaction of allenynes with cis-diazenes (PTAD, 4-phenyl-1,2,4-triazoline-3,5-dione), allowing the practical and efficient synthesis of a diverse array of valuable polycyclic N-heterocycles. A temperature-controlled and stereocontrolled chemoselectivity of the reaction was observed, leading to the chemodivergent synthesis of tetracyclic pyrrolidines, pentacyclic triazepanes and tricyclic pyrrolidines. Compared with related Au-catalyzed cyclization of allenynes, this copper catalysis achieves cyclization of allenynes terminating in C-N bond formation via the HDA reaction.

| S-EPMC10232412 | biostudies-literature

Enantio- and Diastereoselective Synthesis of Functionalized Carbocycles by Cu-Catalyzed Borylative Cyclization of Alkynes with Ketones.

Project description:A single-pot Cu-catalyzed enantio- and diastereoselective tandem hydroboration/borylative cyclization of alkynes with ketones for the synthesis of carbocycles is reported. The reaction proceeds via desymmetrization and generates four contiguous stereocenters, including an all-carbon quaternary center. The method provides rapid access to [6,5]- and [5,5]-bicycles and cyclopentane products. Catalyst-controlled diastereoselectivity by selection of bisphosphine ligand is noted. Utility of the products is demonstrated by site- and chemoselective transformations that afford valuable alkenyl and allyl organoborons.

| S-EPMC6702961 | biostudies-literature

Gold-catalyzed cycloisomerization of 1,5-allenynes via dual activation of an ene reaction.

Project description:Tris(triphenylphosphinegold) oxonium tetrafluoroborate, [(Ph3PAu)3O]BF4, catalyzes the rearrangement of 1,5-allenynes to produce cross-conjugated trienes. Experimental and computational evidence shows that the ene reaction proceeds through a unique nucleophilic addition of an allene double bond to a cationic phosphinegold(I)-complexed phosphinegold(I) acetylide, followed by a 1,5-hydrogen shift.

| S-EPMC2995695 | biostudies-literature

A Tandem Olefin Migration and Prins Cyclization Using Cu(OTf)(2)-Bisphosphine Complexes: An Improved Synthesis of Functionalized Tetrahydropyrans.

Project description:In situ-generated (bis-DPPMB)-Cu(OTf)(2) complex has been examined to catalyze a tandem olefin migration and Prins cyclization of an alkenol with various aldehydes. The reaction proceeded with electron-rich aromatic aldehydes at room temperature and provided functionalized tetrahydropyrans in good yields. An efficient synthesis of the bis-DPPMB ligand has also been described.

| S-EPMC3383828 | biostudies-literature

Triflic-Acid-Catalyzed Tandem Allylic Substitution-Cyclization Reaction of Alcohols with Thiophenols-Facile Access to Polysubstituted Thiochromans.

Project description:Hitherto inaccessible multisubstituted thiochroman derivatives were constructed via the one-pot reaction of thiophenols with allylic alcohols catalyzed by 0.2 equiv triflic acid under metal-free conditions. A variety of thiochroman derivatives can be obtained by this straightforward protocol that allows the introduction of up to four substituents at various locations on the thiochroman skeleton. Relative conformations of all isolated products were confirmed by NOESY NMR studies, and a stepwise mechanism, proceeding via an allylic substitution-intramolecular cyclization protocol, is proposed on the basis of NMR experiments.

| S-EPMC6645051 | biostudies-literature

An Amination-Cyclization Cascade Reaction for Iminosugar Synthesis Using Minimal Protecting Groups.

Project description:The development of a one-step amination-cyclization cascade reaction for the synthesis of N-substituted iminosugars from iodo-pentoses and hexoses is reported. This novel methodology allows for the stereoselective conversion of easily accessible iodo-aldoses and iodo-ketoses into iminosugars in a single step, in highly efficient yields (63-95%), and in aqueous media. Furthermore, the use of functionalized amines allows for the synthesis of N-functionalized iminosugars without additional steps. To illustrate this methodology, a number of biologically important iminosugars were prepared, including 1-deoxynojirimycin, (3S,4R,5S,6R)-azepane-3,4,5,6-tetraol, and N-functionalized 1-deoxymannojirimycins.

| S-EPMC9404175 | biostudies-literature

Palladium-catalyzed oxidative acyloxylation/carbocyclization of allenynes.

Project description: Not available

| S-EPMC3601422 | biostudies-literature