Browse
Submit Data
Databases
API
Help

Dataset Information

34 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Hydroalkylation of Aryl Alkenes with Organohalides Catalyzed by Molybdenum Oxido Based Lewis Pairs.

ABSTRACT: Three molybdenum(VI) dioxido complexes [MoO2(L)2] bearing Schiff base ligands were reacted with B(C6F5)3 to afford the corresponding adducts [MoO{OB(C6F5)3}(L)2], which were fully characterized. They exhibit Frustrated Lewis-Pairs reactivity when reacting with silanes. Especially, the [MoO{OB(C6F5)3}(L)2] complex with L=2,4-dimethyl-6-((phenylimino)methyl)phenol proved to be active as catalyst for the hydroalkylation of aryl alkenes with organohalides and for the Atom-Transfer Radical Addition (ATRA) of organohalides to aliphatic alkenes. A series of gem-dichloride and gem-dibromide compounds with potential for further derivatization were synthesized from simple alkenes and organohalides, like chloroform or bromoform, using low catalyst loading.

SUBMITTER: Zwettler N

PROVIDER: S-EPMC7497237 | biostudies-literature | 2020 Aug

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Hydroalkylation of Aryl Alkenes with Organohalides Catalyzed by Molybdenum Oxido Based Lewis Pairs.

Zwettler Niklas N Dupé Antoine A Klokić Sumea S Milinković Angela A Rodić Dado D Walg Simon S Neshchadin Dmytro D Belaj Ferdinand F Mösch-Zanetti Nadia C NC

Advanced synthesis & catalysis 20200629 15

Three molybdenum(VI) dioxido complexes [MoO2(L)2] bearing Schiff base ligands were reacted with B(C6F5)3 to afford the corresponding adducts [MoO{OB(C6F5)3}(L)2], which were fully characterized. They exhibit Frustrated Lewis-Pairs reactivity when reacting with silanes. Especially, the [MoO{OB(C6F5)3}(L)2] complex with L=2,4-dimethyl-6-((phenylimino)methyl ...[more]

PMID: 32982624

Similar Datasets

Heterolytic Si-H Bond Cleavage at a Molybdenum-Oxido-Based Lewis Pair.

Project description:The reaction of a molybdenum(VI) oxido imido complex with the strong Lewis acid B(C6 F5 )3 gave access to the Lewis adduct [Mo{OB(C6 F5 )3 }(NtBu)L2 ] featuring reversible B-O bonding in solution. The resulting frustrated Lewis pair (FLP)-like reactivity is reflected by the compound's ability to heterolytically cleave Si-H bonds, leading to a clean formation of the novel cationic MoVI species 3 a (R=Et) and 3 b (R=Ph) of the general formula [Mo(OSiR3 )(NtBu)L2 ][HB(C6 F5 )3 ]. These compounds possess properties highly unusual for molybdenum d0 species such as an intensive, charge-transfer-based color as well as a reversible redox couple at very low potentials, both dependent on the silane used. Single-crystal X-ray diffraction analyses of 2 and 4 b, a derivative of 3 b featuring the [FB(C6 F5 )3 ]- anion, picture the stepwise elongation of the Mo=O bond, leading to a large increase in the electrophilicity of the metal center. The reaction of 3 a and 3 b with benzaldehyde allowed for the regeneration of compound 2 by hydrosilylation of the benzaldehyde. NMR spectroscopy suggested an unusual mechanism for the transformation, involving a substrate insertion in the B-H bond of the borohydride anion.

| S-EPMC6001527 | biostudies-literature

Stereoselective Synthesis of Trisubstituted Alkenes via Copper Hydride-Catalyzed Alkyne Hydroalkylation.

Project description:Alkenes are ubiquitous in organic chemistry, yet many classes of alkenes remain challenging to access by current synthetic methodology. Herein, we report a copper hydride-catalyzed approach for the synthesis of Z-configured trisubstituted alkenes with high stereo- and regioselectivity via alkyne hydroalkylation. A DTBM-dppf-supported Cu catalyst was found to be optimal, providing a substantial increase in product yield compared to reactions conducted with dppf as the ligand. DFT calculations show that the DTBM substitution leads to the acceleration of alkyne hydrocupration through combined ground and transition state effects related to preventing catalyst dimerization and enhancing catalyst-substrate dispersion interactions, respectively. Alkyne hydroalkylation was successfully demonstrated with methyl and larger alkyl tosylate electrophiles to produce a variety of (hetero)aryl-substituted alkenes in moderate to high yields with complete selectivity for the Z stereochemically configured products. In the formation of the key C-C bond, computational studies revealed a direct SN2 pathway for alkylation of the vinylcopper intermediate with in situ-formed alkyl iodides.

| S-EPMC10569085 | biostudies-literature

Synthesis of Isomerically Pure (Z)-Alkenes from Terminal Alkynes and Terminal Alkenes: Silver-Catalyzed Hydroalkylation of Alkynes.

Project description:Alkenes are an important class of compounds common among biologically active molecules and often are used as intermediates in organic synthesis. Many alkenes exist in two stereoisomeric forms (E and Z), which have different structures and different properties. The selective formation of the two isomers is an important synthetic goal that has long inspired the development of new synthetic methods. However, the efficient synthesis of diastereopure, thermodynamically less stable, Z-alkenes is still challenging. Here, we demonstrate an efficient synthesis of diastereopure Z-alkenes (Z:E > 300:1) through a silver-catalyzed hydroalkylation of terminal alkynes, using alkylboranes as coupling partners. We also describe the exploration of the substrate scope, which reveals the broad functional group compatibility of the new method. Preliminary mechanistic studies suggest that a 1,2-metalate rearrangement of the silver borate intermediate is the key step responsible for the stereochemical outcome of the reaction.

| S-EPMC7304281 | biostudies-literature

Lewis acid-promoted [2 + 2] cycloadditions of alkenes with aryl ketenes.

Project description:A method for the [2 + 2] cycloaddition of aryl ketenes and alkenes is presented. The process involves the in situ generation of a ketene in the presence of a Lewis acid. The utility of products is demonstrated towards the synthesis of a common scaffold found in several natural product families.

| S-EPMC4814371 | biostudies-literature

Nickel-catalyzed asymmetric reductive aryl-allylation of unactivated alkenes.

Project description:Herein we report a nickel-catalyzed asymmetric reductive aryl-allylation of aryl iodide-tethered unactivated alkenes, wherein both acyclic allyl carbonates and cyclic vinyl ethylene carbonates can serve as the coupling partners. Furthermore, the direct use of allylic alcohols as the electrophilic allyl source in this reaction is also viable in the presence of BOC anhydride. Remarkably, this reaction proceeds with high linear/branched-, E/Z- and enantio-selectivity, allowing the synthesis of various chiral indanes and dihydrobenzofurans (50 examples) containing a homoallyl-substituted quaternary stereocenter with high optical purity (90-98% ee). In this reductive reaction, the use of pregenerated organometallics can be circumvented, giving this process good functionality tolerance and high step-economy.

| S-EPMC8133004 | biostudies-literature

Controlled and Efficient Polymerization of Conjugated Polar Alkenes by Lewis Pairs Based on Sterically Hindered Aryloxide-Substituted Alkylaluminumitle.

Project description:Reported herein is the development of an effective strategy for controlled and efficient Lewis pair polymerization of conjugated polar alkenes, including methyl methacrylate (MMA), n-butyl methacrylate (nBuMA), and γ-methyl-α-methylene-γ-butyrolactone (γMMBL), by the utilization of sterically encumbered Al(BHT)₂Me (BHT: 2,6-di-tert-butyl-4-methylphenol) as a Lewis acid that shuts down intramolecular backbiting termination. In combination with a selected N-heterocyclic carbene (NHC) as a Lewis base, the polymerization of MMA exhibited activity up to 3000 h-1 TOF and an acceptable initiation efficiency of 60.6%, producing polymers with high molecular weight (Mn up to 130 kg/mol) and extremely narrow dispersity (Đ = 1.06~1.13). This controlled polymerization with a living characteristic has been evidenced by chain-extension experiments and chain-end analysis, and enabled the synthesis of well-defined diblock copolymers.

| S-EPMC6017945 | biostudies-literature

Enantioselective Synthesis of γ-Lactams by Lewis Base Catalyzed Sulfenoamidation of Alkenes.

Project description:A method for the catalytic, enantioselective, intramolecular 1,2-sulfenoamidation of alkenes is described. Lewis base activation of a suitable sulfur electrophile generates an enantioenriched, thiiranium ion intermediate from a β,γ-unsaturated sulfonyl carboxamide. This intermediate is subsequently intercepted by the sulfonamide nitrogen resulting in cyclization to form γ-lactams. Electron-poor alkenes required the use of a new selenophosphoramidate Lewis base catalyst. Subsequent manipulations of the products harness the latent reactivity of both the amide and thioether functionality.

| S-EPMC7127933 | biostudies-literature

Synthesis of Carbonyl-Containing Oxindoles via Ni-Catalyzed Reductive Aryl-Acylation and Aryl-Esterification of Alkenes.

Project description:Carbonyl-containing oxindoles are ubiquitous core structures present in many biologically active natural products and pharmaceutical molecules. Nickel-catalyzed reductive aryl-acylation of alkenes using aryl anhydrides or alkanoyl chlorides as acyl sources is developed, providing 3,3-disubstituted oxindoles bearing ketone functionality at the 3-position. Moreover, nickel-catalyzed reductive aryl-esterification of alkenes using chloroformate as ester sources is further developed, affording 3,3-disubstituted oxindoles bearing ester functionality at the 3-position. This strategy has the advantages of good yields and high functional group compatibility.

| S-EPMC9503384 | 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

Enantioselective CuH-Catalyzed Reductive Coupling of Aryl Alkenes and Activated Carboxylic Acids.

Project description:A new method for the enantioselective reductive coupling of aryl alkenes with activated carboxylic acid derivatives via copper hydride catalysis is described. Dual catalytic cycles are proposed, with a relatively fast enantioselective hydroacylation cycle followed by a slower diastereoselective ketone reduction cycle. Symmetrical aryl carboxyclic anhydrides provide access to enantioenriched ?-substituted ketones or alcohols with excellent stereoselectivity and functional group tolerance.

| S-EPMC4866599 | 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