Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Cobalt-catalyzed multisubstituted allylation of the chelation-assisted C-H bond of (hetero)arenes with cyclopropenes.

ABSTRACT: Cyclopropenes are highly strained three-membered carbocycles, which offer unique reactivity in organic synthesis. Herein, Cp*Co^III-catalyzed ring-opening isomerization of cyclopropenes to cobalt vinylcarbene has been utilized for the synthesis of multisubstituted allylarenes via directing group-assisted functionalization of C-H bonds of arenes and heteroarenes. Employing this methodology, various substituents can be introduced at all three carbons of the allyl moiety with high selectivity. The important highlights are excellent functional group tolerance, multisubstituted allylation, high selectivity, gram scale synthesis, removable directing group, and synthesis of cyclopenta[b]indoles. In addition, a potential cobaltocycle intermediate was identified and a plausible mechanism is also proposed.

SUBMITTER: Ramachandran K

PROVIDER: S-EPMC8528013 | biostudies-literature | 2021 Oct

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Cobalt-catalyzed multisubstituted allylation of the chelation-assisted C-H bond of (hetero)arenes with cyclopropenes.

Ramachandran Kuppan K Anbarasan Pazhamalai P

Chemical science 20210915 40

Cyclopropenes are highly strained three-membered carbocycles, which offer unique reactivity in organic synthesis. Herein, Cp*Co<sup>III</sup>-catalyzed ring-opening isomerization of cyclopropenes to cobalt vinylcarbene has been utilized for the synthesis of multisubstituted allylarenes <i>via</i> directing group-assisted functionalization of C-H bonds of arenes and heteroarenes. Employing this methodology, various substituents can be introduced at all three carbons of the allyl moiety with high ...[more]

PMID: 34777763

Similar Datasets

Cobalt-Catalyzed Diastereoselective and Enantioselective Hydrosilylation of Achiral Cyclopropenes.

Project description:A mild diastereoselective and enantioselective cobalt-catalyzed hydrosilylation reaction of achiral cyclopropenes has been developed. In this protocol, various substituted cyclopropenes and arylsilanes were transformed, in the presence of readily available chiral cobalt complex, into silylcyclopropanes with high selectivities.

| S-EPMC7467819 | biostudies-literature

Nickel(IV)-Catalyzed C-H Trifluoromethylation of (Hetero)arenes.

Project description:This Article describes the development of a stable NiIV complex that mediates C(sp2)-H trifluoromethylation reactions. This reactivity is first demonstrated stoichiometrically and then successfully translated to a NiIV-catalyzed C-H trifluoromethylation of electron-rich arene and heteroarene substrates. Both experimental and computational mechanistic studies support a radical chain pathway involving NiIV, NiIII, and NiII intermediates.

| S-EPMC7542544 | biostudies-literature

Hg(OTf)2 Catalyzed Intramolecular 1,4-Addition of Donor-Acceptor Cyclopropenes to Arenes.

Project description:A Hg(OTf)2 catalyzed intramolecular arene 1,4-addition reaction of N-benzyl donor-acceptor cyclopropenecarboxamides was developed to synthesize a series of [3.2.2]nonatriene derivatives. This novel reaction is also observed with silver(I) catalysts known to form metal carbene intermediates in competition with the Buchner reaction.

| S-EPMC5572213 | biostudies-literature

A mild, ferrocene-catalyzed C-H imidation of (hetero)arenes.

Project description:A simple method for direct C-H imidation is reported using a new perester-based self-immolating reagent and a base-metal catalyst. The succinimide products obtained can be easily deprotected in situ (if desired) to reveal the corresponding anilines directly. The scope of the reaction is broad, the conditions are extremely mild, and the reaction is tolerant of oxidizable and acid-labile functionality, multiple heteroatoms, and aryl iodides. Mechanistic studies indicate that ferrocene (Cp2Fe) plays the role of an electron shuttle in the decomposition of the perester reagent, delivering a succinimidyl radical ready to add to an aromatic system.

| S-EPMC4210156 | biostudies-literature

Pd(II)-Catalyzed C3-Selective Arylation of Pyridine with (Hetero)arenes.

Project description:Palladium catalyzed, nondirected C3-selective arylation of pyridines with arenes and heteroarenes in the presence of 1,10-phenanthroline as the ligand has been developed. The optimized conditions allow for a highly C3-selective arylation of pyridines, affording various 3,3'-bipyridines and 3-arylpyridines.

| S-EPMC4821414 | biostudies-literature

Infrared Irradiation-Assisted Solvent-Free Pd-Catalyzed (Hetero)aryl-aryl Coupling via C-H Bond Activation.

Project description:The increasing attention towards environmentally friendly synthetic protocols has boosted studies directed to the development of green and sustainable methods for direct C-H bond arylation of (hetero)arenes. In this context, here the infrared (IR) irradiation-assisted solvent-free Pd-catalyzed direct C-H bond arylation of (hetero)arenes was achieved. Several heteroaryl-aryl coupling reactions were described, also involving heterocycles commonly used as building blocks for the synthesis of organic semiconductors. The reaction tolerated many functional groups on the aromatic nuclei. The IR-irradiation as the energy source compared favorably with thermal heating and, in combination with solvent-free conditions, provided an important contribution to the development of protocols fitting with the principles of green chemistry.

| S-EPMC8456959 | biostudies-literature

Cobalt-catalyzed hydroxymethylarylation of terpenes with formaldehyde and arenes.

Project description:Terpenes, consisting of isoprene monomer units, represent a family of naturally abundant compounds. The difunctionalization of terpenes is highly appealing yet remains challenging, since the multiple unbiased C[double bond, length as m-dash]C bonds of terpenes lead to difficulty in controlling the regioselectivity. Herein, a cobalt(iii)-catalyzed C-H activation strategy has been developed to facilitate hydroxymethylarylation of terpenes with formaldehyde and arenes with high chemo- and regio-selectivities. These (chemo- and regio-) selectivities are governed by the coordination abilities of isoprene, directing groups and the steric effect. This terpene difunctionalization also features high atom and step economy through a C-H addition pathway.

| S-EPMC6979501 | biostudies-literature

Toward Green Acylation of (Hetero)arenes: Palladium-Catalyzed Carbonylation of Olefins to Ketones.

Project description:Green Friedel-Crafts acylation reactions belong to the most desired transformations in organic chemistry. The resulting ketones constitute important intermediates, building blocks, and functional molecules in organic synthesis as well as for the chemical industry. Over the past 60 years, advances in this topic have focused on how to make this reaction more economically and environmentally friendly by using green acylating conditions, such as stoichiometric acylations and catalytic homogeneous and heterogeneous acylations. However, currently well-established methodologies for their synthesis either produce significant amounts of waste or proceed under harsh conditions, limiting applications. Here, we present a new protocol for the straightforward and selective introduction of acyl groups into (hetero)arenes without directing groups by using available olefins with inexpensive CO. In the presence of commercial palladium catalysts, inter- and intramolecular carbonylative C-H functionalizations take place with good regio- and chemoselectivity. Compared to classical Friedel-Crafts chemistry, this novel methodology proceeds under mild reaction conditions. The general applicability of this methodology is demonstrated by the direct carbonylation of industrial feedstocks (ethylene and diisobutene) as well as of natural products (eugenol and safrole). Furthermore, synthetic applications to drug molecules are showcased.

| S-EPMC5785770 | biostudies-literature

Cobalt-catalyzed aminocarbonylation of (hetero)aryl halides promoted by visible light.

Project description:The catalytic aminocarbonylation of (hetero)aryl halides is widely applied in the synthesis of amides but relies heavily on the use of precious metal catalysis. Herein, we report an aminocarbonylation of (hetero)aryl halides using a simple cobalt catalyst under visible light irradiation. The reaction extends to the use of (hetero)aryl chlorides and is successful with a broad range of amine nucleophiles. Mechanistic investigations are consistent with a reaction proceeding via intermolecular charge transfer involving a donor-acceptor complex of the substrate and cobaltate catalyst.

| S-EPMC8159399 | biostudies-literature

Silver-catalyzed regioselective deuteration of (hetero)arenes and α-deuteration of 2-alkyl azaarenes.

Project description:A simple silver-catalyzed regioselective deuteration of (hetero)arenes and α-deuteration of 2-alkyl azaarenes has been described. This strategy provides an efficient and practical avenue to access various deuterated electron-rich arenes, azaarenes and α-deuterated 2-alkyl azaarenes with good to excellent deuterium incorporation utilizing D2O as the source of deuterium atoms.

| S-EPMC9055237 | 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