Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Enantioselective and Diastereodivergent Allylation of Propargylic C-H Bonds.

ABSTRACT: An iridium-catalyzed stereoselective coupling of allylic ethers and alkynes to generate 3,4-substituted 1,5-enynes is reported. Under optimized conditions, the coupling products are formed with excellent regio-, diastereo-, and enantioselectivities, and the protocol is functional group tolerant. Moreover, we report conditions that allow the reaction to proceed with complete reversal of diastereoselectivity. Mechanistic studies are consistent with an unprecedented dual role for the iridium catalyst, enabling the propargylic deprotonation of the alkyne through π-coordination, as well as the generation of a π-allyl species from the allylic ether starting material.

SUBMITTER: Zhu J

PROVIDER: S-EPMC9437123 | biostudies-literature | 2022 Aug

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Enantioselective and Diastereodivergent Allylation of Propargylic C-H Bonds.

Zhu Jin J Wang Yidong Y Charlack Aaron D AD Wang Yi-Ming YM

Journal of the American Chemical Society 20220817 34

An iridium-catalyzed stereoselective coupling of allylic ethers and alkynes to generate 3,4-substituted 1,5-enynes is reported. Under optimized conditions, the coupling products are formed with excellent regio-, diastereo-, and enantioselectivities, and the protocol is functional group tolerant. Moreover, we report conditions that allow the reaction to proceed with complete reversal of diastereoselectivity. Mechanistic studies are consistent with an unprecedented dual role for the iridium cataly ...[more]

PMID: 35976157

Similar Datasets

Enantioselective Allylation of Stereogenic Nitrogen Centers.

Project description:Most tertiary amines with a stereogenic nitrogen center undergo rapid racemization at room temperature. Consequently, the quaternization of amines under dynamic kinetic resolution seems feasible. N-Methyl tetrahydroisoquinolines are converted into configurationally stable ammonium ions by Pd-catalyzed allylic alkylation. The optimization of conditions and the evaluation of the substrate scope enabled high conversions and an enantiomeric ratio of up to 10:90. We report here the first examples for the enantioselective catalytic synthesis of chiral ammonium ions.

| S-EPMC10028698 | biostudies-literature

Enantioselective conjugate allylation of cyclic enones.

Project description:Enantioselective organocatalytic 1,2-allylation of a cyclic enone followed by anionic oxy-Cope rearrangement delivered the ketone as a mixture of diastereomers. This appears to be a general method for the net enantioselective conjugate allylation of cyclic enones.

| S-EPMC3237403 | biostudies-literature

Rhodium-catalyzed enantioselective and diastereodivergent access to diaxially chiral heterocycles.

Project description:N-N axially chiral biaryls represent a rarely explored class of atropisomers. Reported herein is construction of diverse classes of diaxially chiral biaryls containing N-N and C-N/C-C diaxes in distal positions in excellent enantioselectivity and diastereoselectivity. The N-N chiral axis in the products provides a handle toward solvent-driven diastereodivergence, as has been realized in the coupling of a large scope of benzamides and sterically hindered alkynes, affording diaxes in complementary diastereoselectivity. The diastereodivergence has been elucidated by computational studies which revealed that the hexafluoroisopropanol (HFIP) solvent molecule participated in an unusual manner as a solvent as well as a ligand and switched the sequence of two competing elementary steps, resulting in switch of the stereoselectivity of the alkyne insertion and inversion of the configuration of the C-C axis. Further cleavage of the N-directing group in the diaxial chiral products transforms the diastereodivergence to enantiodivergence.

| S-EPMC10400608 | biostudies-literature

Iridium-Catalyzed Enantioselective Intermolecular Indole C2-Allylation.

Project description:The enantioselective intermolecular C2-allylation of 3-substituted indoles is reported for the first time. This directing group-free approach relies on a chiral Ir-(P, olefin) complex and Mg(ClO4 )2 Lewis acid catalyst system to promote allylic substitution, providing the C2-allylated products in typically high yields (40-99 %) and enantioselectivities (83-99 % ee) with excellent regiocontrol. Experimental studies and DFT calculations suggest that the reaction proceeds via direct C2-allylation, rather than C3-allylation followed by in situ migration. Steric congestion at the indole-C3 position and improved π-π stacking interactions have been identified as major contributors to the C2-selectivity.

| S-EPMC7217203 | biostudies-literature

Regioselective and enantioselective propargylic hydroxylations catalyzed by P450tol monooxygenases.

Project description:Regioselective and enantioselective hydroxylation of propargylic C-H bonds are useful reactions but often lack appropriate catalysts. Here a green and efficient asymmetric hydroxylation of primary and secondary C-H bonds at propargylic positions has been established. A series of optically active propargylic alcohols were prepared with high regio- and enantioselectivity (up to 99% ee) under mild reaction conditions by using P450tol, while the C≡C bonds in the molecule remained unreacted. This protocol provides a green and practical method for constructing enantiomerically chiral propargylic alcohols. In addition, we also demonstrated that the biohydroxylation strategy was able to scaled up to 2.25 mmol scale with the production of chiral propargyl alcohol 2a at a yield of 196 mg with 96% ee, which's an important synthetic intermediate of antifungal drug Ravuconazole.

| S-EPMC11219674 | biostudies-literature

Bi(III)-Catalyzed Enantioselective Allylation Reactions of Ketimines.

Project description:Chiral homoallylic amines not only are found in pharmaceutically relevant compounds but also serve as versatile building blocks for chemical synthesis. However, catalytic allylation of ketimines with allylboronates, an attractive approach to synthesize chiral homoallylic amine scaffolds remain scarce. Herein, we develop a highly enantioselective allylation of isatin-derived ketimines with boron allylation reagents catalyzed by a Bi(OAc)3-chiral phosphoric acid catalyst system. The reactions are remarkably efficient and mild, most of which were completed in less than an hour at room temperature with only 1/2 mol% (Bi(OAc)3/CPA) catalyst loading. A wide range of chiral 3-allyl 3-aminooxindoles were obtained in excellent yields and enantioselectivities. The synthetic utility was demonstrated by efficient formal synthesis of (+)-AG-041R and (-)-psychotriasine. Preliminary mechanism was studied by control experiments and theoretical calculations.

| S-EPMC6593186 | biostudies-literature

Catalytic enantioselective conjugate allylation of unsaturated methylidene ketones.

Project description:The use of unsaturated methylidene ketones in catalytic conjugate allylations allows a significant expansion in substrate scope and, with appropriate chiral ligands, occurs in a highly enantioselective fashion.

| S-EPMC3065356 | biostudies-literature

Iridium-catalyzed regioselective and enantioselective allylation of trimethylsiloxyfuran.

Project description:We report the regio- and enantioselective allylation of an ester enolate, trimethylsiloxyfuran. This enolate reacts at the 3-position with linear aromatic allylic carbonates or aliphatic allylic benzoates to form the branched substitution products in the presence of a metallacyclic iridium catalyst. This process provides access to synthetically important 3-substituted butenolides in enantioenriched form. Stoichiometric reactions of the allyliridium intermediate suggest that the trimethylsiloxyfuran is activated by the carboxylate leaving group.

| S-EPMC3487469 | biostudies-literature

Enantioselective Allylation Using Allene, a Petroleum Cracking Byproduct.

Project description:Allene (C3H4) gas is produced and separated on million-metric-ton scale per year during petroleum refining but is rarely employed in organic synthesis. Meanwhile, the addition of an allyl group (C3H5) to ketones is among the most common and prototypical reactions in synthetic chemistry. Herein, we report that the combination of allene gas with inexpensive and environmentally benign hydrosilanes, such as PMHS, can serve as a replacement for stoichiometric quantities of allylmetal reagents, which are required in most enantioselective ketone allylation reactions. This process is catalyzed by copper salts and commercially available ligands, operates without specialized equipment or pressurization, and tolerates a broad range of functional groups. Furthermore, the exceptional chemoselectivity of this catalyst system enables industrially relevant C3 hydrocarbon mixtures of allene with methylacetylene and propylene to be applied directly.

| S-EPMC6497157 | biostudies-literature

Iridium-Catalyzed Enantioselective Propargylic C-H Trifluoromethylthiolation and Related Processes.

Project description:The trifluoromethylthio group (SCF3) has gained increasing prominence in the field of drug design and development due to its unique electronic properties, remarkable stability, and high lipophilicity, but its derivatives remain challenging to access, especially in an enantioselective manner. In this Communication, we present an enantioselective iridium-catalyzed trifluoromethylthiolation of the propargylic C(sp3)-H bonds of alkynes. This protocol demonstrates its efficacy across a diverse array of alkyne substrates, including B- and Si-protected terminal alkynes as well as those derived from natural products and pharmaceuticals, to give trifluoromethyl thioethers with good to excellent yield and stereoselectivity. Moreover, this protocol could be modified to access enantioenriched difluoromethyl and chlorodifluoromethyl thioethers (SCF2H and SCF2Cl derivatives), significantly expanding the space of synthetically accessible enantioenriched fluoroorganic compounds.

| S-EPMC11487557 | 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