Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Highly Stereoselective Intermolecular Haloetherification and Haloesterification of Allyl Amides.

ABSTRACT: An organocatalytic and highly regio-, diastereo-, and enantioselective intermolecular haloetherification and haloesterification reaction of allyl amides is reported. A variety of alkene substituents and substitution patterns are compatible with this chemistry. Notably, electronically unbiased alkene substrates exhibit exquisite regio- and diastereoselectivity for the title transformation. We also demonstrate that the same catalytic system can be used in both chlorination and bromination reactions of allyl amides with a variety of nucleophiles with little or no modification.

SUBMITTER: Soltanzadeh B

PROVIDER: S-EPMC4874786 | biostudies-literature | 2015 Aug

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Highly Stereoselective Intermolecular Haloetherification and Haloesterification of Allyl Amides.

Soltanzadeh Bardia B Jaganathan Arvind A Staples Richard J RJ Borhan Babak B

Angewandte Chemie (International ed. in English) 20150625 33

An organocatalytic and highly regio-, diastereo-, and enantioselective intermolecular haloetherification and haloesterification reaction of allyl amides is reported. A variety of alkene substituents and substitution patterns are compatible with this chemistry. Notably, electronically unbiased alkene substrates exhibit exquisite regio- and diastereoselectivity for the title transformation. We also demonstrate that the same catalytic system can be used in both chlorination and bromination reaction ...[more]

PMID: 26110812

Similar Datasets

Highly Regio- and Enantioselective Vicinal Dihalogenation of Allyl Amides.

Project description:We report a highly regio-, diastereo- and enantioselective vicinal dihalogenation of allyl amides. E- and Z-alkenes with both aryl and alkyl substituents were compatible with this chemistry. This is the result of exquisite catalyst controlled regioselectivity enabling use of electronically unbiased substrates. The reaction employs commercially available catalysts and halenium sources along with cheap inorganic halide salts to affect this transformation. A preliminary effort to extend this chemistry to heterodihalogenation is also presented.

| S-EPMC7790169 | biostudies-literature

Highly chemoselective synthesis of hindered amides via cobalt-catalyzed intermolecular oxidative hydroamidation.

Project description:α-Tertiary amides are of great importance for medicinal chemistry. However, they are often challenging to access through conventional methods due to reactivity and chemoselectivity issues. Here, we report a single-step approach towards such amides via cobalt-catalyzed intermolecular oxidative hydroamidation of unactivated alkenes, using nitriles of either solvent- or reagent-quantities. This protocol is selective for terminal alkenes over groups that rapidly react under known carbocation amidation conditions such as tertiary alcohols, electron-rich alkenes, ketals, weak C-H bonds, and carboxylic acids. Straightforward access to a diverse array of hindered amides is demonstrated, including a rapid synthesis of an aminoadamantane-derived pharmaceutical intermediate.

| S-EPMC8100129 | biostudies-literature

Chemoselective Intermolecular Cross-Enolate-Type Coupling of Amides.

Project description:A new approach for the synthesis of 1,4-dicarbonyl compounds is reported. Chemoselective activation of amide carbonyl functionality and subsequent umpolung via N-oxide addition generates an electrophilic enolonium species that can be coupled with a wide range of nucleophilic enolates. The method conveys broad functional group tolerance on both components, does not suffer from formation of homocoupling byproducts and avoids the use of transition metal catalysts.

| S-EPMC5691317 | biostudies-literature

Stereoselective synthesis of spirooxindole amides through nitrile hydrozirconation.

Project description:Spirooxindole amides can be prepared by the intramolecular addition of functionalized indoles into acylimines that are accessed from nitriles by hydrozirconation and acylation. The stereochemical outcome at the quaternary center was controlled by the steric bulk of the substituent at the 2-position of the indole unit. The products are well-suited for diversification to prepare libraries.

| S-EPMC2980567 | biostudies-literature

Stereoselective Gold(I)-Catalyzed Intermolecular Hydroalkoxlation of Alkynes.

Project description:We report the use of cationic gold complexes [Au(NHC)(CH3CN)][BF4] and [{Au(NHC)}2(?-OH)][BF4] (NHC = N-heterocyclic carbene) as highly active catalysts in the solvent-free hydroalkoxylation of internal alkynes using primary and secondary alcohols. Using this simple protocol, a broad range of (Z)-vinyl ethers were obtained in excellent yields and high stereoselectivities. The methodology allows for the use of catalyst loadings as low as 200 ppm for the addition of primary alcohols to internal alkynes (TON = 35 000, TOF = 2188 h-1).

| S-EPMC5745073 | biostudies-literature

Chemo- and Stereoselective Transition-Metal-Free Amination of Amides with Azides.

Project description:The synthesis of α-amino carbonyl/carboxyl compounds is a contemporary challenge in organic synthesis. Herein, we present a stereoselective α-amination of amides employing simple azides that proceeds under mild conditions with release of nitrogen gas. The amide is used as the limiting reagent, and through simple variation of the azide pattern, various differently substituted aminated products can be obtained. The reaction is fully chemoselective for amides even in the presence of esters or ketones and lends itself to preparation of optically enriched products.

| S-EPMC4945995 | biostudies-literature

Development of a polarizable intermolecular potential function (PIPF) for liquid amides and alkanes.

Project description:A polarizable intermolecular potential function (PIPF) employing the Thole interacting dipole (TID) polarization model has been developed for liquid alkanes and amides. In connection with the internal bonding terms of the CHARMM22 force field, the present PIPF-CHARMM potential provides an adequate description of structural and thermodynamic properties for liquid alkanes and for liquid amides through molecular dynamics simulations. The computed heats of vaporization and liquid density are within 1.4% of experimental values. Polarization effects play a major role in liquid amides, which are reflected by an increase of 1.5 to 1.8 D in molecular dipole moment for primary and secondary amides. Furthermore, the computed polarization energies contribute to the total intermolecular interaction energy by 6 to 24%. The ability of the PIPF-CHARMM force field to treat protein backbone structures is tested by examining the potential energy surface of the amide bond rotation in N-methylacetamide and the Ramachandran surface for alanine dipeptide. The agreement with ab initio MP2 results and with the original CHARMM22 force field is encouraging, suggesting the PIPF-CHARMM potential can be used as a starting point to construct a complete polarizable force field for proteins.

| S-EPMC2572772 | biostudies-other

Biocatalytic, Intermolecular C-H Bond Functionalization for the Synthesis of Enantioenriched Amides.

Project description:Directed evolution of heme proteins has opened access to new-to-nature enzymatic activity that can be harnessed to tackle synthetic challenges. Among these, reactions resulting from active site iron-nitrenoid intermediates present a powerful strategy to forge C-N bonds with high site- and stereoselectivity. Here we report a biocatalytic, intermolecular benzylic C-H amidation reaction operating at mild and scalable conditions. With hydroxamate esters as nitrene precursors, feedstock aromatic compounds can be converted to chiral amides with excellent enantioselectivity (up to >99 % ee) and high yields (up to 87 %). Kinetic and computational analysis of the enzymatic reaction reveals rate-determining nitrenoid formation followed by stepwise hydrogen atom transfer-mediated C-H functionalization.

| S-EPMC8578410 | biostudies-literature

Gold-catalyzed intermolecular coupling of sulfonylacetylene with allyl ethers: [3,3]- and [1,3]-rearrangements.

Project description:Gold-catalyzed intermolecular couplings of sulfonylacetylenes with allyl ethers are reported. A cooperative polarization of alkynes both by a gold catalyst and a sulfonyl substituent resulted in an efficient intermolecular tandem carboalkoxylation. Reactions of linear allyl ethers are consistent with the [3,3]-sigmatropic rearrangement mechanism, while those of branched allyl ethers provided [3,3]- and [1,3]-rearrangement products through the formation of a tight ion-dipole pair.

| S-EPMC3778381 | biostudies-literature

Isomerization of N-Allyl Amides To Form Geometrically Defined Di-, Tri-, and Tetrasubstituted Enamides.

Project description:Enamides represent bioactive pharmacophores in various natural products, and have become increasingly common reagents for asymmetric incorporation of nitrogen functionality. Yet the synthesis of the requisite geometrically defined enamides remains problematic, especially for highly substituted and Z-enamides. Herein we wish to report a general atom economic method for the isomerization of a broad range of N-allyl amides to form Z-di-, tri-, and tetrasubstituted enamides with exceptional geometric selectivity. This report represents the first examples of a catalytic isomerization of N-allyl amides to form nonpropenyl disubstituted, tri- and tetrasubstituted enamides with excellent geometric control. Applications of these geometrically defined enamides toward the synthesis of cis vicinal amino alcohols and tetrasubstituted α-borylamido complexes are discussed.

| S-EPMC5726938 | 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