Browse
Submit Data
Databases
API
Help

Dataset Information

30 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Nickel-catalyzed coupling of alkenes, aldehydes, and silyl triflates.

ABSTRACT: A full account of two recently developed nickel-catalyzed coupling reactions of alkenes, aldehydes, and silyl triflates is presented. These reactions provide either allylic alcohol or homoallylic alcohol derivatives selectively, depending on the ligand employed. These processes are believed to be mechanistically distinct from Lewis acid-catalyzed carbonyl-ene reactions, and several lines of evidence supporting this hypothesis are discussed.

SUBMITTER: Ng SS

PROVIDER: S-EPMC3148200 | biostudies-literature | 2006 Sep

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Nickel-catalyzed coupling of alkenes, aldehydes, and silyl triflates.

Ng Sze-Sze SS Ho Chun-Yu CY Jamison Timothy F TF

Journal of the American Chemical Society 20060901 35

A full account of two recently developed nickel-catalyzed coupling reactions of alkenes, aldehydes, and silyl triflates is presented. These reactions provide either allylic alcohol or homoallylic alcohol derivatives selectively, depending on the ligand employed. These processes are believed to be mechanistically distinct from Lewis acid-catalyzed carbonyl-ene reactions, and several lines of evidence supporting this hypothesis are discussed. ...[more]

PMID: 16939275

Similar Datasets

Nickel-Catalyzed Defluorinative Coupling of Aliphatic Aldehydes with Trifluoromethyl Alkenes.

Project description:A simple procedure is reported for the nickel-catalyzed defluorinative alkylation of unactivated aliphatic aldehydes. The process involves the catalytic reductive union of trifluoromethyl alkenes with aldehydes using a nickel complex of a 6,6'-disubstituted bipyridine ligand with zinc metal as the terminal reductant. The protocol is distinguished by its broad substrate scope, mild conditions, and simple catalytic setup. Reaction outcomes are consistent with the intermediacy of an α-silyloxy(alkyl)nickel intermediate generated by a low-valent nickel catalyst, silyl electrophile, and the aldehyde substrate. Mechanistic findings with cyclopropanecarboxaldehyde provide insights into nature of the reactive intermediates and illustrate fundamental reactivity differences that are governed by subtle changes in ligand and substrate structure.

| S-EPMC9390876 | biostudies-literature

The First Example of Nickel-Catalyzed Silyl-Heck Reactions: Direct Activation of Silyl Triflates Without Iodide Additives.

Project description:For the first time, nickel-catalyzed silyl-Heck reactions are reported. Using simple phosphine-supported nickel catalysts, direct activation of silyl triflates has been achieved. These results contrast earlier palladium-catalyzed systems, which require iodide additives to activate silyl-triflates. These nickel-based catalysts exhibit good functional group tolerance in the preparation of vinyl silanes, and unlike earlier systems, allows for the incorporation of trialkylsilanes larger than Me3Si.

| S-EPMC4047519 | biostudies-literature

Nickel-catalyzed Kumada cross-coupling reactions of tertiary alkylmagnesium halides and aryl bromides/triflates.

Project description:We report a Ni-catalyzed process for the cross-coupling of tertiary alkyl nucleophiles and aryl bromides. This process is extremely general for a wide range of electrophiles and generally occurs with a ratio of retention to isomerization >30:1. The same procedure also accommodates the use of aryl triflates, vinyl chlorides, and vinyl bromides as the electrophilic component.

| S-EPMC8036247 | biostudies-literature

Zinc(II) catalyzed conversion of alkynes to vinyl triflates in the presence of silyl triflates.

Project description:The conversion of alkynes to their corresponding vinyl triflates in the presence of stoichiometric TMS-triflate was greatly facilitated by the triflate salt of several transition metal catalysts most especially Zn(OTf)2. Products are formed in high regioselectivity under mild conditions. Internal alkynes bearing an aryl substituent afford vinyl triflates with a modest preference for the Z-isomer especially with larger substituents. A mechanism is put forward to explain the unique role of silicon in this system.

| S-EPMC4136703 | biostudies-literature

Nickel-catalyzed dehydrogenative cross-coupling: direct transformation of aldehydes into esters and amides.

Project description:By exploring a new mode of nickel-catalyzed cross-coupling, a method to directly transform both aromatic and aliphatic aldehydes into either esters or amides has been developed. The success of this oxidative coupling depends on the appropriate choice of catalyst and organic oxidant, including the use of either ?,?,?-trifluoroacetophenone or excess aldehyde. Mechanistic data that supports a catalytic cycle involving oxidative addition into the aldehyde C-H bond is also presented.

| S-EPMC4551080 | biostudies-literature

Enantioselective Redox-Neutral Coupling of Aldehydes and Alkenes by an Iron-Catalyzed "Catch-Release" Tethering Approach.

Project description:The reductive coupling of aldehydes and alkenes is an emerging technology that holds the potential to reinvent carbonyl addition chemistry. However, existing enantioselective methods are limited to form "branched" products. Herein, we present a directed enantio- and diastereoselective alkylation of aldehydes with simple olefins to selectively yield linear coupling products. This is achieved by redox-neutral remote functionalization, whereby a tethering "catch-release" strategy decisively solves the key problems of reactivity and selectivity.

| S-EPMC6342409 | biostudies-literature

Nickel-Catalyzed Conversion of Enol Triflates into Alkenyl Halides.

Project description:A Ni-catalyzed halogenation of enol triflates was developed and it enables the synthesis of a broad range of alkenyl iodides, bromides, and chlorides under mild reaction conditions. The reaction utilizes inexpensive, bench-stable Ni(OAc)2 ?4?H2 O as a precatalyst and proceeds at room temperature in the presence of sub-stoichiometric Zn and either 1,5-cyclooctadiene or 4-(N,N-dimethylamino)pyridine.

| S-EPMC7179072 | biostudies-literature

A palladium-catalyzed three-component cross-coupling of conjugated dienes or terminal alkenes with vinyl triflates and boronic acids.

Project description:A three-component coupling of vinyl triflates and boronic acids to alkenes catalyzed by palladium is reported. Using 1,3-dienes, selective 1,2-alkene difunction-alization is observed, whereas the use of terminal alkenes results in 1,1-alkene difunctionalization. The reaction outcome is attributed to the formation of stabilized, cationic Pd-?-allyl intermediates to regulate ?-hydride elimination.

| S-EPMC3084658 | biostudies-literature

Nickel-catalyzed allylic substitution of simple alkenes.

Project description:This report describes a nickel-catalyzed allylic substitution process of simple alkenes whereby an important structural motif, a 1,4-diene, was prepared. The key to success is the use of an appropriate nickel-phosphine complex and a stoichiometric amount of silyl triflate. Reactions of 1-alkyl-substituted alkenes consistently provided 1,1-disubstituted alkenes with high selectivity. Insight into the reaction mechanism as well as miscellaneous application of the developed catalytic process is also documented.

| S-EPMC3224962 | biostudies-literature

Nickel-Catalyzed Stereoselective Arylboration of Unactivated Alkenes.

Project description:A Ni-catalyzed method for arylboration is disclosed. The method allows for highly stereoselective arylboration of unactivated alkenes. The reactions utilize a simple Ni-catalyst and work with a broad range of alkenes and aryl bromides. The products represent useful intermediates for chemical synthesis due to the versatility of the C-B bond. Preliminary mechanistic details of the method are also disclosed.

| S-EPMC5778876 | 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