Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Iron-Catalyzed Borylation of Propargylic Acetates for the Synthesis of Multisubstituted Allenylboronates.

ABSTRACT: A novel iron-catalyzed borylation of propargylic acetates leading to allenylboronates has been developed. The method allows the preparation of a variety of di-, tri- and tetrasubstituted allenylboronates at room temperature with good functional group compatibility. Stereochemical studies show that an anti-S_N 2' displacement of acetate by boron occurs; this also allows transfer of chirality to yield enantiomerically enriched allenylboronates. The synthetic utility of this protocol was further substantiated by transformations of the obtained allenylboronates including oxidation and propargylation.

SUBMITTER: Bermejo-Lopez A

PROVIDER: S-EPMC10099795 | biostudies-literature | 2023 Jan

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Iron-Catalyzed Borylation of Propargylic Acetates for the Synthesis of Multisubstituted Allenylboronates.

Bermejo-López Aitor A Kong Wei-Jun WJ Tortajada Pedro J PJ Posevins Daniels D Martín-Matute Belén B Bäckvall Jan-E JE

Chemistry (Weinheim an der Bergstrasse, Germany) 20221122 3

A novel iron-catalyzed borylation of propargylic acetates leading to allenylboronates has been developed. The method allows the preparation of a variety of di-, tri- and tetrasubstituted allenylboronates at room temperature with good functional group compatibility. Stereochemical studies show that an anti-S<sub>N</sub> 2' displacement of acetate by boron occurs; this also allows transfer of chirality to yield enantiomerically enriched allenylboronates. The synthetic utility of this protocol was ...[more]

PMID: 36250587

Similar Datasets

Iron-catalyzed carbometalation of propargylic and homopropargylic alcohols.

Project description:Nucleophilic addition to alkynes represents an attractive approach to the synthesis of olefins. Obstacles to this strategy include the low reactivity of alkynes toward many organometallic reagents and difficulties associated with controlling the regioselectivity of addition. Here we demonstrate that Fe(III) salts are effective precatalysts for the carbometalation of alkynes. Primary and secondary propargylic and homopropargylic alcohols react with alkyl and aryl Grignard reagents to provide Z-allylic and -homoallylic alcohols as single stereo and regioisomers. Alkylation and arylation occur distal to the alcohol. Common oxygen protecting groups and tertiary nitrogens are tolerated. The intermediate vinyl magnesium or iron species can be trapped with a variety of electrophiles including aldehydes, allyl bromide, and N-bromosuccinimide. Diyne substrates undergo an unusual addition/cyclization reaction to generate cyclic dienes. A brief discussion of mechanism is included.

| S-EPMC2536518 | biostudies-literature

Stereocontrol in Palladium-Catalyzed Propargylic Substitutions: Kinetic Resolution to give Enantioenriched 1,5-Enynes and Propargyl Acetates.

Project description:Kinetic resolution during the catalytic allyl-propargyl cross-coupling with chiral starting materials can be accomplished with a chiral Palladium catalyst. These reactions offer ready access to enantiomerically enriched enyne products from simple readily available starting materials.

| S-EPMC4019443 | biostudies-literature

Rh-Catalyzed Cascade C-H Activation/Annulation of N-Hydroxybenzamides and Propargylic Acetates for Modular Access to Isoquinolones

Project description:A sequential Rh(III)-catalyzed C-H activation/annulation of N-hydroxybenzamides with propargylic acetates leading to the formation of NH-free isoquinolones is described. This reaction proceeds through a sequential C-H activation/alkyne insertion/intramolecular annulation/N-O bond cleavage procedure, affording a broad spectrum of products with diverse substituents in moderate-to-excellent yields. Notably, this protocol features the simultaneous formation of two new C-C/C-N bonds and one heterocycle in one pot with the release of water as the sole byproduct.

| S-EPMC9740102 | biostudies-literature

Transition-Metal-Free Borylation of Allylic and Propargylic Alcohols.

Project description:The base-catalyzed allylic borylation of tertiary allylic alcohols allows the synthesis of 1,1-disubstituted allyl boronates, in moderate to high yield. The unexpected tandem performance of the Lewis acid-base adduct, [Hbase](+) [MeO-B2 pin2 ](-) favored the formation of 1,2,3-triborylated species from the tertiary allylic alcohols and 1-propargylic cyclohexanol at 90 °C.

| S-EPMC4804746 | biostudies-literature

Metal-catalyzed [1,2]-alkyl shift in allenyl ketones: synthesis of multisubstituted furans.

Project description: Not available

| S-EPMC3684434 | biostudies-literature

Pt(II)-catalyzed synthesis of 1,2-dihydropyridines from aziridinyl propargylic esters.

Project description:Pt(II)-catalyzed cycloisomerization of aziridinyl propargylic esters affords 1,2-dihydropyridines with regiodefined installation of substituents. A mild conversion of the 1,2-dihydropyridines to the corresponding substituted pyridines as well as chirality retention from the aziridinyl propargylic ester substrates have been demonstrated.

| S-EPMC3384524 | biostudies-literature

Light-promoted borylation and lactonization of propargyl acetates using NHC-borane.

Project description:In the absence of photoredox catalyst (PC), we have successfully achieved radical borylation and lactonization of propargyl acetates under light irradiation using N-heterocyclic carbene borane (NHC-borane), leading to the synthesis of various substituted 4-(NHC-boryl)-2(5H)-furanones. The reaction is triggered from the generation of an NHC-boryl radical, which is formed via hydrogen atom transfer (HAT) of NHC-borane with tert-butyl peroxide derived from the light-induced homolytic cleavage of di-tert-butyl peroxide (DTPB). During the lactonization process, carbon boron formation, carbon-carbon bond formation and cleavage are observed. This approach offers a facile and mild method for the construction of borylated furanones, opening a new possibility in radical borylation chemistry.

| S-EPMC11812365 | biostudies-literature

Phosphine-catalyzed [4+2] annulations of 2-alkylallenoates and olefins: synthesis of multisubstituted cyclohexenes.

Project description:From our investigations on phosphine-catalyzed [4+2] annulations between α-alkyl allenoates and activated olefins for the synthesis of cyclohexenes, we discovered a hexamethylphosphorous triamide (HMPT)-catalyzed [4+2] reaction between α-alkyl allenoates 1 and arylidene malonates or arylidene cyanoacetates 2 that provides highly functionalized cyclohexenes 3 and 4 in synthetically useful yields (30-89%), with moderate to exclusive regioselectivity, and reasonable diastereoselectivity. Interestingly, the [4+2] annulations between the α-alkyl allenoates 1 and the olefins 2 manifested a polarity inversion of the 1,4-dipole synthon 1, depending on the structure of the olefin, thus providing cyclohexenes 3 exclusively when using arylidene cyanoacetates. The polarity inversion of α-alkyl allenoates from a 1,4-dipole A to B under phosphine catalysis can be explained by an equilibrium between the phosphonium dienolate C and the phosphorous ylide D.

| S-EPMC4122298 | biostudies-literature

Cu-Catalyzed Decarboxylative Borylation.

Project description:A simple method for the conversion of carboxylic acids to boronic esters via redox-active esters (RAEs) is reported using copper catalysis. The scope of this transformation is broad, and compared with the known protocols available, it represents the most inexpensive, rapid, and operationally simple option. In addition to a full exploration of the scope, a kinetic study was performed to elucidate substrate and reagent concentration dependences.

| S-EPMC6257631 | biostudies-literature

Collective synthesis of acetylenic pharmaceuticals via enantioselective Nickel/Lewis acid-catalyzed propargylic alkylation.

Project description:Chiral acetylenic derivatives are found in many bioactive compounds and are versatile functional groups in organic chemistry. Here, we describe an enantioselective nickel/Lewis acid-catalyzed asymmetric propargylic substitution reaction from simple achiral materials under mild condition. The introduction of a Lewis acid cocatalyst is crucial to the efficiency of the transformation. Notably, we investigate this asymmetric propargylic substitution reaction for the development of a range of structurally diverse natural products. The power of this strategy is highlighted by the collective synthesis of seven biologically active compounds: (-)-Thiohexital, (+)-Thiopental, (+)-Pentobarbital, (-)-AMG 837, (+)-Phenoxanol, (+)-Citralis, and (-)-Citralis Nitrile.

| S-EPMC7803749 | 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