Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Photocatalytic Radical Aroylation of Unactivated Alkenes: Pathway to β-Functionalized 1,4-, 1,6-, and 1,7-Diketones.

ABSTRACT: We report the development of a photocatalytic strategy for the synthesis of β-functionalized unsymmetrical 1,4-, 1-6 and 1,7-diketones from aroyl chlorides and unactivated alkenes at room temperature. The mild reaction conditions not only tolerate a wide range of functional groups and structural moieties, but also enable migration of a variety of distal groups including (hetero)arenes, nitrile, aldehyde, oxime-derivative, and alkene. The efficiency of chirality transfer, factors that control the distal-group migration, and synthesis of carbo- and heterocycles from the diketones are also described. Mechanistic studies suggest a reaction pathway involving a photocatalytic radical aroylation of unactivated alkenes followed by a distal-group migration, oxidation, and deprotonation to afford the desired diketones.

SUBMITTER: Sarkar S

PROVIDER: S-EPMC8147874 | biostudies-literature | 2019 Nov

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Photocatalytic Radical Aroylation of Unactivated Alkenes: Pathway to β-Functionalized 1,4-, 1,6-, and 1,7-Diketones.

Sarkar Satavisha S Banerjee Arghya A Yao Wang W Patterson Eric V EV Ngai Ming-Yu MY

ACS catalysis 20191017 11

We report the development of a photocatalytic strategy for the synthesis of β-functionalized unsymmetrical 1,4-, 1-6 and 1,7-diketones from aroyl chlorides and unactivated alkenes at room temperature. The mild reaction conditions not only tolerate a wide range of functional groups and structural moieties, but also enable migration of a variety of distal groups including (hetero)arenes, nitrile, aldehyde, oxime-derivative, and alkene. The efficiency of chirality transfer, factors that control the ...[more]

PMID: 34040817

Similar Datasets

Synthesis of Ketonylated Carbocycles via Excited-State Copper-Catalyzed Radical Carbo-Aroylation of Unactivated Alkenes.

Project description:Carbocycles are core skeletons in natural and synthetic organic compounds possessing a wide diversity of important biological activities. Herein, we report the development of an excited-state copper-catalyzed radical carbo-aroylation of unactivated alkenes to synthesize ketonylated tetralins, di- and tetrahydrophenanthrenes, and cyclopentane derivatives. The reaction is operationally simple and features mild reaction conditions that tolerate a broad range of functional groups. Preliminary mechanistic studies suggest a reaction pathway beginning with photoexcitation of [CuI-BINAP]2 and followed by a single electron transfer (SET), radical aroylation of unactivated alkenes, radical cyclization, and re-aromatization, affording the desired ketonylated carbocycles.

| S-EPMC10723085 | biostudies-literature

Photocatalytic radical defluoroalkylation of unactivated alkenes via distal heteroaryl ipso-migration.

Project description:Currently, the selective activation of C(sp3)-F bonds and C-C bonds constitute one of the most widely used procedures for the synthesis of high-value products that range from pharmaceuticals to agrochemical applications. While numerous examples of these two methods have been reported in their respective fields, the processes which merge the activation of both single C(sp3)-F bonds and C-C bonds in one step still remain elusive. Here, we demonstrate the controllable defluoroalkylation-distal functionalization of trifluoromethylarenes with unactivated alkenes via distal heteroaryl migration. This is proposed to proceed via tandem C(sp3)-F and C-C bond cleavage using visible-light photoredox catalysis combined with Lewis acid activation. This strategy provides facile and flexible access to multiply functionalized α,α-difluorobenzylic ketones in useful yields (up to 88%) under mild conditions. The products can be further transformed into other valuable compounds, demonstrating the method's utility.

| S-EPMC9814454 | biostudies-literature

Base-Promoted Radical Azofluoromethylation of Unactivated Alkenes.

Project description:The base-induced reaction of aryl diazonium salts with commercially available CF3SO2Na/CF2HSO2Na allows for the generation of the corresponding diazene radicals along with fluoromethyl radicals. The addition of fluoromethyl radicals to alkenes with subsequent diazene trapping provides the azofluoromethylation products in good to excellent yields. This metal-free method under mild reaction conditions has broad functional group compatibility and is applicable in the late-stage modification of various natural products and bioactive molecules.

| S-EPMC7328341 | biostudies-literature

Radical 1-Fluorosulfonyl-2-alkynylation of Unactivated Alkenes.

Project description:Sulfonyl fluorides have found widespread use in chemical biology and drug discovery. The development of synthetic methods for the introduction of the sulfonyl fluoride moiety is therefore of importance. Herein, a transition-metal-free radical 1,2-difunctionalization of unactivated alkenes via FSO2 -radical addition with subsequent vicinal alkynylation to access β-alkynyl-fluorosulfonylalkanes is presented. Alkynyl sulfonyl fluorides are introduced as highly valuable bifunctional radical trapping reagents that also serve as FSO2 -radical precursors. The β-alkynyl-fluorosulfonylalkanes obtained in these transformations can be readily diversified by using SuFEx click chemistry to obtain sulfonates and sulfonamides.

| S-EPMC9305502 | biostudies-literature

Radical chain repair: The hydroalkylation of polysubstituted unactivated alkenes.

Project description:The concept of repair is widely used by nature to heal molecules such as proteins, lipids, sugars, and DNA that are damaged by hydrogen atom abstraction resulting from oxidative stress. We show that this strategy, rather undocumented in the field of synthetic organic chemistry, can be used in a radical chain reaction to enable notoriously intractable transformations. By overcoming the radical chain inhibitor properties of substituted alkenes, the radical-mediated hydroalkylation of mono-, di-, tri-, and even tetrasubstituted unactivated olefins could be performed under mild conditions. With a remarkable functional group tolerance, this reaction provides a general coupling method for the derivatization of olefin-containing natural products.

| S-EPMC6054511 | biostudies-literature

Carboamination of Unactivated Alkenes through Three-Component Radical Conjugate Addition.

Project description:Two-component Giese type radical additions are highly practical and established reactions. Herein, three-component radical conjugate additions of unactivated alkenes to Michael acceptors are reported. Amidyl radicals, oxidatively generated from α-amido oxy acids using redox catalysis, act as the third reaction component which add to the unactivated alkenes. The adduct radicals engage in Giese type additions to Michael acceptors to provide, after reduction, the three-component products in an overall alkene carboamination reaction. Transformations which can be conducted under practical mild conditions feature high functional group tolerance and broad substrate scope.

| S-EPMC6900080 | biostudies-literature

Fe(III)/NaBH4-mediated free radical hydrofluorination of unactivated alkenes.

Project description:A powerful Fe(III)/NaBH(4)-mediated free radical hydrofluorination of unactivated alkenes is disclosed using Selectfluor reagent as a source of fluorine and resulting in exclusive Markovnikov addition. In contrast to the traditional and unmanageable free radical hydrofluorination of alkenes, the Fe(III)/NaBH(4)-mediated reaction is conducted under exceptionally mild reaction conditions (0 °C, 5 min, CH(3)CN/H(2)O). The reaction can be conducted open to the air and with water as a cosolvent and demonstrates an outstanding substrate scope and functional group tolerance.

| S-EPMC3425717 | biostudies-literature

β-Selective Aroylation of Activated Alkenes by Photoredox Catalysis.

Project description:Late-stage synthesis of α,β-unsaturated aryl ketones remains an unmet challenge in organic synthesis. Reported herein is a photocatalytic non-chain-radical aroyl chlorination of alkenes by a 1,3-chlorine atom shift to form β-chloroketones as masked enones that liberate the desired enones upon workup. This strategy suppresses side reactions of the enone products. The reaction tolerates a wide array of functional groups and complex molecules including derivatives of peptides, sugars, natural products, nucleosides, and marketed drugs. Notably, addition of 2,6-di-tert-butyl-4-methyl-pyridine enhances the quantum yield and efficiency of the cross-coupling reaction. Experimental and computational studies suggest a mechanism involving PCET, formation and reaction of an α-chloro-α-hydroxy benzyl radical, and 1,3-chlorine atom shift.

| S-EPMC6527503 | biostudies-literature

Photocatalytic 1,3-difluoroalkylcarboxylation of alkenes by triple kinetic-controlled radical self-ordering.

Project description:A transition-metal-free protocol for the unsymmetrical radical 1,3-difunctionalization of alkenes has been established for the first time in the form of 1,3-difluoroalkylcarboxylation by a photocatalytic radical three-component reaction of allyl formates, trifluoroacetanilides, and cesium formate. This reaction employs formate as the carboxylating reagent and trifluoroacetanilide as the difluoroalkylating reagent via C-F bond activation. As a result, a series of previously inaccessible unsymmetrical difluorinated adipic acid derivatives can be easily and efficient prepared. Mechanism studies reveal that triple kinetic-controlled radical self-ordering is the key to this unique reaction. This radical sorting involves the fast initiation of a CO2 radical anion and its chemoselective addition and reduction, followed by the slow generation of a fluoroalkyl radical and its chemo-/regioselective addition. Notably, this strategy is also suitable for the 1,3-difluoroalkylcarboxylation of unsymmetrical and cyclic alkenes through diastereoselectively constructing two or three consecutive stereocenters.

| S-EPMC11878238 | biostudies-literature

Radical Hydroarylation of Functionalized Olefins and Mechanistic Investigation of Photocatalytic Pyridyl Radical Reactions.

Project description:We report the photoredox alkylation of halopyridines using functionalized alkene and alkyne building blocks. Selective single-electron reduction of the halogenated pyridines provides the corresponding heteroaryl radicals, which undergo anti-Markovnikov addition to the alkene substrates. The system is shown to be mild and tolerant of a variety of alkene and alkyne subtypes. A combination of computational and experimental studies support a mechanism involving proton-coupled electron transfer followed by medium-dependent alkene addition and rapid hydrogen atom transfer mediated by a polarity-reversal catalyst.

| S-EPMC6495588 | 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