Browse
Submit Data
Databases
API
Help

Dataset Information

95 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Organophotoredox-Catalyzed Formation of Alkyl-Aryl and -Alkyl C-S/Se Bonds from Coupling of Redox-Active Esters with Thio/Selenosulfonates.

ABSTRACT: A mild organophotoredox synthetic protocol for forming a C_sp³-S/Se bond by reacting widespread redox-active esters with thio/selenosulfonates has been developed. The power of the synthetic manifold is fueled by an unprecedented broad substrate scope and wide functional group tolerance.

SUBMITTER: Dong Y

PROVIDER: S-EPMC7936573 | biostudies-literature | 2020 Dec

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Organophotoredox-Catalyzed Formation of Alkyl-Aryl and -Alkyl C-S/Se Bonds from Coupling of Redox-Active Esters with Thio/Selenosulfonates.

Dong Yue Y Ji Peng P Zhang Yueteng Y Wang Changqing C Meng Xiang X Wang Wei W

Organic letters 20201210 24

A mild organophotoredox synthetic protocol for forming a C<sub>sp<sup>3</sup></sub>-S/Se bond by reacting widespread redox-active esters with thio/selenosulfonates has been developed. The power of the synthetic manifold is fueled by an unprecedented broad substrate scope and wide functional group tolerance. ...[more]

PMID: 33300807

Similar Datasets

Practical Ni-Catalyzed Aryl-Alkyl Cross-Coupling of Secondary Redox-Active Esters.

Project description:A new transformation is presented that enables chemists to couple simple alkyl carboxylic acids with aryl zinc reagents under Ni-catalysis. The success of this reaction hinges on the unique use of redox-active esters that allow one to employ such derivatives as alkyl halides surrogates. The chemistry exhibits broad substrate scope and features a high degree of practicality. The simple procedure and extremely inexpensive nature of both the substrates and pre-catalyst (NiCl2·6H2O, ca. $9.5/mol) bode well for the immediate widespread adoption of this method.

| S-EPMC4768290 | biostudies-literature

Iron-catalyzed cross-coupling of unactivated secondary alkyl thio ethers and sulfones with aryl Grignard reagents.

Project description:The first systematic investigation of unactivated aliphatic sulfur compounds as electrophiles in transition-metal-catalyzed cross-coupling are described. Initial studies focused on discerning the structural and electronic features of the organosulfur substrate that enable the challenging oxidative addition to the C(sp(3))-S bond. Through extensive optimization efforts, an Fe(acac)3-catalyzed cross-coupling of unactivated alkyl aryl thio ethers with aryl Grignard reagents was realized in which a nitrogen "directing group" on the S-aryl moiety of the thio ether served a critical role in facilitating the oxidative addition step. In addition, alkyl phenyl sulfones were found to be effective electrophiles in the Fe(acac)3-catalyzed cross-coupling with aryl Grignard reagents. For the latter class of electrophile, a thorough assessment of the various reaction parameters revealed a dramatic enhancement in reaction efficiency with an excess of TMEDA (8.0 equiv). The optimized reaction protocol was used to evaluate the scope of the method with respect to both the organomagnesium nucleophile and sulfone electrophile.

| S-EPMC3913001 | biostudies-literature

A general alkyl-alkyl cross-coupling enabled by redox-active esters and alkylzinc reagents.

Project description:Alkyl carboxylic acids are ubiquitous in all facets of chemical science, from natural products to polymers, and represent an ideal starting material with which to forge new connections. This study demonstrates how the same activating principles used for decades to make simple C-N (amide) bonds from carboxylic acids with loss of water can be used to make C-C bonds through coupling with dialkylzinc reagents and loss of carbon dioxide. This disconnection strategy benefits from the use of a simple, inexpensive nickel catalyst and exhibits a remarkably broad scope across a range of substrates (>70 examples).

| S-EPMC4867118 | biostudies-literature

Redox-Active Esters in Fe-Catalyzed C-C Coupling.

Project description:Cross-couplings of alkyl halides and organometallic species based on single electron transfer using Ni and Fe catalyst systems have been studied extensively, and separately, for decades. Here we demonstrate the first couplings of redox-active esters (both isolated and derived in situ from carboxylic acids) with organozinc and organomagnesium species using an Fe-based catalyst system originally developed for alkyl halides. This work is placed in context by showing a direct comparison with a Ni catalyst for >40 examples spanning a range of primary, secondary, and tertiary substrates. This new C-C coupling is scalable and sustainable, and it exhibits a number of clear advantages in several cases over its Ni-based counterpart.

| S-EPMC5016806 | biostudies-literature

Iron-Catalyzed Cross-Coupling Reactions of Alkyl Grignards with Aryl Chlorobenzenesulfonates.

Project description:Aryl sulfonate esters are versatile synthetic intermediates in organic chemistry as well as attractive architectures due to their bioactive properties. Herein, we report the synthesis of alkyl-substituted benzenesulfonate esters by iron-catalyzed C(sp2)-C(sp3) cross-coupling of Grignard reagents with aryl chlorides. The method operates using an environmentally benign and sustainable iron catalytic system, employing benign urea ligands. A broad range of chlorobenzenesulfonates as well as challenging alkyl organometallics containing β-hydrogens are compatible with these conditions, affording alkylated products in high to excellent yields. The study reveals that aryl sulfonate esters are the most reactive activating groups for iron-catalyzed alkylative C(sp2)-C(sp3) cross-coupling of aryl chlorides with Grignard reagents.

| S-EPMC8510395 | biostudies-literature

Nickel-Catalyzed Cross-Coupling of Redox-Active Esters with Boronic Acids.

Project description:A transformation analogous in simplicity and functional group tolerance to the venerable Suzuki cross-coupling between alkyl-carboxylic acids and boronic acids is described. This Ni-catalyzed reaction relies upon the activation of alkyl carboxylic acids as their redox-active ester derivatives, specifically N-hydroxy-tetrachlorophthalimide (TCNHPI), and proceeds in a practical and scalable fashion. The inexpensive nature of the reaction components (NiCl2 ⋅6 H2 O-$9.5 mol(-1) , Et3 N) coupled to the virtually unlimited commercial catalog of available starting materials bodes well for its rapid adoption.

| S-EPMC5232357 | biostudies-literature

Nickel-Catalyzed Cross-Electrophile Coupling of Aryl Chlorides with Primary Alkyl Chlorides.

Project description:Alkyl chlorides and aryl chlorides are among the most abundant and stable carbon electrophiles. Although their coupling with carbon nucleophiles is well developed, the cross-electrophile coupling of aryl chlorides with alkyl chlorides has remained a challenge. We report here the first general approach to this transformation. The key to productive, selective cross-coupling is the use of a small amount of iodide or bromide along with a recently reported ligand, pyridine-2,6-bis(N-cyanocarboxamidine) (PyBCamCN). The scope of the reaction is demonstrated with 35 examples (63 ± 16% average yield), and we show that the Br- and I- additives act as cocatalysts, generating a low, steady-state concentration of more-reactive alkyl bromide/iodide.

| S-EPMC7418462 | biostudies-literature

Palladium-Catalyzed Decarbonylative Coupling of (Hetero)Aryl Boronate Esters with Difluorobenzyl Glutarimides.

Project description:This report describes the Pd-catalyzed decarbonylative coupling of difluorobenzyl glutarimides with (hetero)aryl boronate esters to yield difluorobenzyl-substituted (hetero)arene products. The use of PAd2Bu as the phosphine ligand in combination with neopentylboronate ester nucleophiles proved critical for the selective formation of the decarbonylative coupling product versus analogous difluorobenzyl ketone. This transformation is effective for electronically diverse (hetero)aryl boronate esters and substituted difluorobenzyl glutarimides.

| S-EPMC10629228 | biostudies-literature

Synthesis of Fluorinated Alkyl Aryl Ethers by Palladium-Catalyzed C-O Cross-Coupling.

Project description:Herein, we report a highly effective protocol for the cross-coupling of (hetero)aryl bromides with fluorinated alcohols using the commercially available precatalyst tBuBrettPhos Pd G3 and Cs2CO3 in toluene. This Pd-catalyzed coupling features a short reaction time, excellent functional group tolerance, and compatibility with electron-rich and -poor (hetero)arenes. The method provides access to 18F-labeled trifluoroethyl ethers by cross-coupling with [18F]trifluoroethanol.

| S-EPMC7458480 | biostudies-literature

Nickel-catalyzed cross-coupling of potassium aryl- and heteroaryltrifluoroborates with unactivated alkyl halides.

Project description:A method for the cross-coupling of alkyl electrophiles with various potassium aryl- and heteroaryltrifluoroborates has been developed. Nearly stoichiometric amounts of organoboron species could be employed to cross-couple a large variety of challenging heteroaryl nucleophiles. Several functional groups were tolerated on both the electrophilic and the nucleophilic partners. Chemoselective reactivity of C(sp(3))-Br bonds in the presence of C(sp(2))-Br bonds was achieved.

| S-EPMC3075421 | 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