Browse
Submit Data
Databases
API
Help

Dataset Information

20 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Three-Step Telescoped Synthesis of Monosubstituted Vicinal Diamines from Aldehydes.

ABSTRACT: Aldehydes are easily transformed into vicinal diamines and piperazines through a one-pot procedure including a Darzens reaction and treatment with an amine or diamine and then with a reducing agent. Additionally, quinoxalines can be accessed by reaction with 1,2-benzenediamine under oxidative conditions. These transformations are simple methods for the preparation of synthetically interesting monosubstituted diamines, piperazines, and quinoxalines.

SUBMITTER: Bou-Iserte L

PROVIDER: S-EPMC6648690 | biostudies-literature | 2019 Jan

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Three-Step Telescoped Synthesis of Monosubstituted Vicinal Diamines from Aldehydes.

Bou-Iserte Lledó L Latorre Antonio A Rodríguez Santiago S González Florenci V FV

ACS omega 20190129 1

Aldehydes are easily transformed into vicinal diamines and piperazines through a one-pot procedure including a Darzens reaction and treatment with an amine or diamine and then with a reducing agent. Additionally, quinoxalines can be accessed by reaction with 1,2-benzenediamine under oxidative conditions. These transformations are simple methods for the preparation of synthetically interesting monosubstituted diamines, piperazines, and quinoxalines. ...[more]

PMID: 31459468

Similar Datasets

Three step synthesis of single diastereoisomers of the vicinal trifluoro motif.

Project description:A three step route to single diastereoisomers of the vicinal trifluoromethyl motif is described. The route starts from either syn- or anti-alpha,beta-epoxy alcohols and takes a direct approach in that each of the three steps introduces a fluorine atom in a regio- and stereo-specific manner. Starting from either the syn- or the anti-alpha,beta-epoxy alcohol, stereospecific reactions generate two separate diastereoisomeric series of this motif. The route is a significant improvement on an earlier six step strategy.

| S-EPMC2839549 | biostudies-literature

Chiral Vicinal Diamines Derived from Mefloquine.

Project description:Novel 1,2-diamines based on the mefloquine scaffold prepared in enantiomerically pure forms resemble 9-amino-Cinchona alkaloids. Most effectively, 11-aminomefloquine with an erythro configuration was obtained by conversion of 11-alcohol into azide and hydrogenation. Alkylation of a secondary amine unit was needed to arrive at diastereomeric threo-11-aminomefloquine and to introduce diversity. Most of the substitution reactions of the hydroxyl group to azido group proceeded with net retention of the configuration and involved actual aziridine or plausible aziridinium ion intermediates. Enantiomerically pure products were obtained by the resolution of either the initial mefloquine or one of the final products. The evaluation of the efficacy of the obtained vicinal diamines in enantioselective transformations proved that erythro-11-aminomefloquine is an effective catalyst in the asymmetric Michael addition of nitromethane to cyclohexanone (up to 96.5:3.5 er) surpassing epi-aminoquinine in terms of selectivity.

| S-EPMC8389910 | biostudies-literature

Process Safety Assessment of the Iron-Catalyzed Direct Olefin Diazidation for the Expedient Synthesis of Vicinal Primary Diamines.

Project description:We report herein a process safety assessment of the iron-catalyzed direct olefin diazidation for the preparation of a broad range of synthetically valuable vicinal primary diamines. Differential scanning calorimetry analysis of the corresponding reagents, intermediates, and a list of representative diazide/diaminium salt products revealed that all of them are thermal stable at the reaction temperature. The drop weight test of the diazides suggested that they are moderately impact-sensitive. Guided by this assessment, an optimized olefin diazidation/diamination procedure has been developed which allows for the gram-scale diaminium salt synthesis without purification of the diazide intermediate.

| S-EPMC5773106 | biostudies-literature

Ring Opening of Aziridines by Pendant Sulfamates Allows for Regioselective and Stereospecific Preparation of Vicinal Diamines.

Project description:The ring opening of aziridines by pendant sulfamates is a viable strategy for the rapid preparation of vicinal diamines. Our reaction is compatible with both disubstituted cis- and trans-aziridines; unsubstituted, N-alkyl, and N-aryl sulfamates engage effectively. In all cases examined, the cyclization reaction is perfectly regioselective and stereospecific. Once activated, the product oxathiazinane heterocycles can be ring opened with a diverse range of nucleophiles.

| S-EPMC10799289 | biostudies-literature

Three-component coupling reactions of silylglyoxylates, alkynes, and aldehydes: a chemoselective one-step glycolate aldol construction.

Project description:A single-pot three-component coupling reaction of silylglyoxylates (1), terminal alkynes, and aldehydes in the presence of ZnI2 and Et3N is presented. The products of the reaction, densely functionalized silyl-protected glycolate aldols (2), can be converted to the corresponding acetonides (3) in a one-pot deprotection/ketalization sequence. A variety of terminal alkynes and aldehydes can be successfully employed to give a range of highly functionalized, fully protected 1,2-diols in good yields and moderate diastereoselectivities. Mechanistic experiments suggest that the zinc acetylide reacts with the silylgyloxylate (1) in a chemoselective manner. Using an unoptimized (+)-N-methylephedrine and Zn(OTf)2 system, silyl-deprotected adduct 2 was formed in 64% ee and 89:11 dr.

| S-EPMC2827871 | biostudies-literature

Homologated amino acids with three vicinal fluorines positioned along the backbone: development of a stereoselective synthesis.

Project description:Backbone-extended amino acids have a variety of potential applications in peptide and protein science, particularly if the geometry of the amino acid is controllable. Here we describe the synthesis of δ-amino acids that contain three vicinal C-F bonds positioned along the backbone. The ultimately successful synthetic approach emerged through the investigation of several methods based on both electrophilic and nucleophilic fluorination chemistry. We show that different diastereoisomers of this fluorinated δ-amino acid adopt distinct conformations in solution, suggesting that these molecules might have value as shape-controlled building blocks for future applications in peptide science.

| S-EPMC5687047 | biostudies-literature

New synthesis of tetraoxaspirododecane-diamines and tetraoxazaspirobicycloalkanes.

Project description:An efficient method for the synthesis of new spiro-tetraoxadodecanediamines and tetraoxazaspirobicycloalkanes has been developed by reactions of primary arylamines with gem-dihydroperoxides and α,ω-dialdehydes (glyoxal, pentanedial) catalyzed by lanthanide catalysts. A potential pathway for formation of tetraoxaspirododecane-diamines and tetraoxazospirobicycloalkanes has been proposed that involves generation of intermediate tetraoxaspiroalkanediols under the reaction conditions. The structures of the crystalline products have been confirmed by XRD. It was shown that the synthesized tetraoxazaspirobicycloalkanes exhibit high cytotoxic activity against Jurkat, K562, and U937 tumor cultures and Fibroblasts.

| S-EPMC9072112 | biostudies-literature

Three-Step Synthesis of the Antiepileptic Drug Candidate Pynegabine.

Project description:Pynegabine, an antiepileptic drug candidate in phase I clinical trials, is a structural analog of the marketed drug retigabine with improved chemical stability, strong efficacy, and a better safety margin. The reported shortest synthetic route for pynegabine contains six steps and involves the manipulation of highly toxic methyl chloroformate and dangerous hydrogen gas. To improve the feasibility of drug production, we developed a concise, three-step process using unconventional methoxycarbonylation and highly efficient Buchwald-Hartwig cross coupling. The new synthetic route generated pynegabine at the decagram scale without column chromatographic purification and avoided the dangerous manipulation of hazardous reagents.

| S-EPMC10343641 | biostudies-literature

The organocatalytic three-step total synthesis of (+)-frondosin B.

Project description:The frondosins are a family of marine sesquiterpenes isolated from the sponge Dysidea frondosa that exhibit biological activities ranging from anti-inflammatory properties to potential application in anticancer and HIV therapy. Herein, a concise enantioselective total synthesis of (+)-frondosin B is described which requires a total of three chemical steps. The enantioselective conjugate addition of a benzofuran-derived boronic acid to crotonaldehyde in the presence of an imidazolidinone organocatalyst builds the critical stereogenic center of frondosin B in the first operation, while the remaining two ring systems of this natural product are installed in the two subsequent steps. A combination of X-ray crystallographic data, deuterium labeling, and chemical correlation studies provides further evidence as to the correct absolute stereochemical assignment of (+)-frondosin B.

| S-EPMC3268339 | biostudies-literature

Ultrasound-assisted synthesis of water-soluble monosubstituted diruthenium compounds.

Project description:The elusive monosubstituted diruthenium complexes [Ru2Cl(DAniF)(O2CMe)3] (1), [Ru2Cl(DPhF)(O2CMe)3] (2), [Ru2Cl(D-p-CNPhF)(O2CMe)3] (3), [Ru2Cl(D-o-TolF)(O2CMe)3] (4), [Ru2Cl(D-m-TolF)(O2CMe)3] (5), [Ru2Cl(D-p-TolF)(O2CMe)3] (6) and [Ru2Cl(p-TolA)(O2CMe)3] (7) have been synthesized using for the first time ultrasound-assisted synthesis to carry out a substitution reaction in metal-metal bonded dinuclear compounds (DAniF- = N,N'-bis(4-anisyl)formamidinate; DPhF- = N,N'-diphenylformamidinate; D-p-CNPhF- = N,N'-bis(4-cyanophenyl)formamidinate; D-o/m/p-TolF- = N,N'-bis(2/3/4-tolyl)formamidinate; p-TolA- = N-4-tolylamidate). This is a simpler and greener method than the tedious procedures described in the literature, and it has permitted to obtain water-soluble complexes with good yields in a short period of time. A synthetic study has been implemented to find the best experimental conditions to prepare compounds 1-7. Two different types of ligands, formamidinate and amidate, have been used to check the generality of the method for the preparation of monosubstituted complexes. Five new compounds (2-6) have been obtained using a formamidinate ligand, the synthesis of the previously described compound 1 has been improved, and an unprecedented monoamidate complex has been achieved (7). The crystal structures of compounds 3 and 7 have been solved by single crystal X-ray diffraction. These compounds show the typical paddlewheel structure with three acetate ligands and one formamidinate (3) or amidate (7) bridging ligand at the equatorial positions. The axial positions are occupied by the chloride ligand giving rise to one-dimensional polymer structures that were previously unknown for monosubstituted compounds.

| S-EPMC8605285 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data