Browse
Submit Data
Databases
API
Help

Dataset Information

19 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Diastereoselective and Enantioselective Conjunctive Cross-Coupling Enabled by Boron Ligand Design.

ABSTRACT: Enantio- and diastereoselective conjunctive cross-coupling of ?-substituted alkenylboron "ate" complexes is studied. Whereas ?-substitution shifts the chemoselectivity of the catalytic reaction in favor of the Suzuki-Miyaura product, use of a boronic ester ligand derived from acenaphthoquinone allows the process to favor the conjunctive product, even with substituted substrates.

SUBMITTER: Myhill JA

PROVIDER: S-EPMC6414218 | biostudies-literature | 2018 Nov

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Diastereoselective and Enantioselective Conjunctive Cross-Coupling Enabled by Boron Ligand Design.

Myhill Jesse A JA Wilhelmsen Christopher A CA Zhang Liang L Morken James P JP

Journal of the American Chemical Society 20181106 45

Enantio- and diastereoselective conjunctive cross-coupling of β-substituted alkenylboron "ate" complexes is studied. Whereas β-substitution shifts the chemoselectivity of the catalytic reaction in favor of the Suzuki-Miyaura product, use of a boronic ester ligand derived from acenaphthoquinone allows the process to favor the conjunctive product, even with substituted substrates. ...[more]

PMID: 30376317

Similar Datasets

Nickel-Catalyzed Enantioselective Conjunctive Cross-Coupling of 9-BBN Borates.

Project description:Catalytic enantioselective conjunctive cross-coupling between 9-BBN borate complexes and aryl electrophiles can be accomplished with Ni salts in the presence of a chiral diamine ligand. The reactions furnish chiral 9-BBN derivatives in an enantioselective fashion and these are converted to chiral alcohols and amines, or engaged in other stereospecific C-C bond forming reactions.

| S-EPMC5699474 | biostudies-literature

Enantioselective Construction of Tertiary Boronic Esters by Conjunctive Cross-Coupling.

Project description:Catalytic enantioselective conjunctive cross-coupling has been developed to construct tertiary alkylboronic esters. These reactions occur with good yield and enantioselectivity for a range of substrates. Mechanistic experiments reveal aspects of the catalytic cycle that allow hindered substrates to react without significant complicating side reactions.

| S-EPMC6414220 | biostudies-literature

Catalytic Enantioselective Synthesis of anti-Vicinal Silylboronates by Conjunctive Cross-Coupling.

Project description:Chiral 1,2-bimetallic reagents are useful motifs in synthetic chemistry. Although syn-1,2-bimetallic compounds can be prepared by alkene dimetallation, anti-1,2-bimetallics are still rare. The stereospecific 1,2-metallate shift that occurs during conjunctive cross-coupling is shown to enable a practical and modular approach to the catalytic synthesis of enantioenriched anti-1,2-borosilanes. In addition to reaction development, the synthetic utility of anti-1,2-borosilanes was investigated, including applications to the synthesis of anti-1,2-diols and anti-1,2-amino alcohols.

| S-EPMC7359638 | biostudies-literature

Diastereo- and Enantioselective 1,4-Difunctionalization of Borylenynes by Catalytic Conjunctive Cross-Coupling.

Project description:Enantioselective conjunctive cross-coupling of enyne-derived boronate complexes occurs with 1,4 addition of the electrophile and migrating group across the π system. This reaction pathway furnishes α-boryl allenes as the reaction product. In the presence of a chiral catalyst, both the central and axial chirality of the product can be controlled during product formation.

| S-EPMC7473481 | biostudies-literature

Ligand-enabled Ir-catalyzed intermolecular diastereoselective and enantioselective allylic alkylation of 3-substituted indoles.

Project description:An Ir-catalyzed asymmetric allylic alkylation of 3-substituted indoles is reported. The reaction provides indoline products containing multiple contiguous stereocenters with high site-, regio-, diastereo- and enantioselectivities in one step from a wide range of readily available starting materials. The key to this method is the high level of diastereocontrol enabled by an iridium catalyst derived from a N-aryl phosphoramidite ligand (Me-THQphos, 1c).

| S-EPMC5666512 | biostudies-literature

Enantioselective Conjunctive Cross-Coupling of Bis(alkenyl)borates: A General Synthesis of Chiral Allylboron Reagents.

Project description:Palladium-catalyzed conjunctive cross-coupling is used for the synthesis of enantioenriched allylboron reagents. This reaction employs nonsymmetric bis(alkenyl)borates as substrates and appears to occur by a mechanism that involves selective activation of the less substituted alkene followed by migration of the more substituted alkene during the course of a Pd-induced metalate rearrangement.

| S-EPMC5620124 | biostudies-literature

Catalytic Enantioselective Synthesis of β-Allenyl Boronic Esters by Conjunctive Cross-Coupling with Propargylic Carbonates.

Project description:Enantioselective conjunctive cross-coupling with propargylic carbonates affords (β-boryl allenes as the reaction product. The reaction is found to proceed through the intermediacy of dimethoxyboronate complexes that are generated in situ by a strain-induced ligand exchange reaction.

| S-EPMC7943035 | biostudies-literature

Enantioselective Radical Addition/Cross-Coupling of Organozinc Reagents, Alkyl Iodides, and Alkenyl Boron Reagents.

Project description:A hybrid transition-metal/radical process is described that results in the addition of organozinc reagents and alkyl halides across alkenyl boron reagents in an enantioselective catalytic fashion. The reaction can be accomplished both intermolecularly and intramolecularly, providing useful product yields and high enantioselectivities in both manifolds.

| S-EPMC6764867 | biostudies-literature

Integrating Allyl Electrophiles into Nickel-Catalyzed Conjunctive Cross-Coupling.

Project description:Allylation and conjunctive cross-coupling represent two useful, yet largely distinct, reactivity paradigms in catalysis. The union of these two processes would offer exciting possibilities in organic synthesis but remains largely unknown. Herein, we report the use of allyl electrophiles in nickel-catalyzed conjunctive cross-coupling with a non-conjugated alkene and dimethylzinc. The transformation is enabled by weakly coordinating, monodentate aza-heterocycle directing groups that are useful building blocks in synthesis, including saccharin, pyridones, pyrazoles, and triazoles. The reaction occurs under mild conditions and is compatible with a wide range of allyl electrophiles. High chemoselectivity through substrate directivity is demonstrated by the facile reactivity of the β-γ alkene of the starting material, whereas the ϵ-ζ alkene of the product is preserved. The generality of this approach is further illustrated through the development of an analogous method with alkyne substrates. Mechanistic studies reveal the importance of the dissociation of the weakly coordinating directing group to allow the allyl moiety to bind and facilitate C(sp3 )-C(sp3 ) reductive elimination.

| S-EPMC7184930 | biostudies-literature

Ligand-enabled cross-coupling of C(sp(3))-H bonds with arylsilanes.

Project description:Pd(II)-catalyzed cross-coupling of C(sp(3))-H bonds with organosilicon coupling partners has been achieved for the first time. The use of a newly developed quinoline-based ligand is essential for the cross-coupling reactions to proceed.

| S-EPMC4432906 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

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