Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Metal-free hydrogenation catalyzed by an air-stable borane: use of solvent as a frustrated Lewis base.

ABSTRACT: In recent years 'frustrated Lewis pairs' (FLPs) have been shown to be effective metal-free catalysts for the hydrogenation of many unsaturated substrates. Even so, limited functional-group tolerance restricts the range of solvents in which FLP-mediated reactions can be performed, with all FLP-mediated hydrogenations reported to date carried out in non-donor hydrocarbon or chlorinated solvents. Herein we report that the bulky Lewis acids B(C6Cl5)x(C6F5)(3-x) (x=0-3) are capable of heterolytic H2 activation in the strong-donor solvent THF, in the absence of any additional Lewis base. This allows metal-free catalytic hydrogenations to be performed in donor solvent media under mild conditions; these systems are particularly effective for the hydrogenation of weakly basic substrates, including the first examples of metal-free catalytic hydrogenation of furan heterocycles. The air-stability of the most effective borane, B(C6Cl5)(C6F5)2, makes this a practically simple reaction method.

SUBMITTER: Scott DJ

PROVIDER: S-EPMC4497615 | biostudies-literature | 2014 Sep

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Facile Protocol for Water-Tolerant "Frustrated Lewis Pair"-Catalyzed Hydrogenation.

Project description:Despite rapid advances in the field of metal-free, "frustrated Lewis pair" (FLP)-catalyzed hydrogenation, the need for strictly anhydrous reaction conditions has hampered wide-scale uptake of this methodology. Herein, we report that, despite the generally perceived moisture sensitivity of FLPs, 1,4-dioxane solutions of B(C6F5)3 actually show appreciable moisture tolerance and can catalyze hydrogenation of a range of weakly basic substrates without the need for rigorously inert conditions. In particular, reactions can be performed directly in commercially available nonanhydrous solvents without subsequent drying or use of internal desiccants.

| S-EPMC4613738 | biostudies-literature

Chemoselective Hydrogenation of Nitroarenes Using an Air-Stable Base-Metal Catalyst.

Project description:The reduction of nitroarenes to anilines as well as azobenzenes to hydrazobenzenes using a single base-metal catalyst is reported. The hydrogenation reactions are performed with an air-and moisture-stable manganese catalyst and proceed under relatively mild reaction conditions. The transformation tolerates a broad range of functional groups, affording aniline derivatives and hydrazobenzenes in high yields. Mechanistic studies suggest that the reaction proceeds via a bifunctional activation involving metal-ligand cooperative catalysis.

| S-EPMC8041384 | biostudies-literature

A Strategy to Control the Reactivation of Frustrated Lewis Pairs from Shelf-Stable Carbene Borane Complexes.

Project description:N-Phosphine oxide substituted imidazolylidenes (PoxIms) have been synthesized and fully characterized. These species can undergo significant changes to the spatial environment surrounding their carbene center through rotation of the phosphine oxide moiety. Either classical Lewis adducts (CLAs) or frustrated Lewis pairs (FLPs) are thus formed with B(C6 F5 )3 depending on the orientation of the phosphine oxide group. A strategy to reactivate FLPs from CLAs by exploiting molecular motions that are responsive to external stimuli has therefore been developed. The reactivation conditions were successfully controlled by tuning the strain in the PoxIm-B(C6 F5 )3 complexes so that reactivation only occurred above ambient temperature.

| S-EPMC4600235 | biostudies-literature

Geminal bis-borane formation by borane Lewis acid induced cyclopropyl rearrangement and its frustrated Lewis pair reaction with carbon dioxide.

Project description:Cyclopropylacetylene reacts with two molar equivalents of Piers' borane [HB(C6F5)2] under mild conditions by an addition/rearrangement sequence with cyclopropyl ring opening to give a mixture of two α-B(C6F5)2 substituted tetrahydroboroles. This compound forms an active frustrated Lewis pair with P t Bu3 that heterolytically splits dihydrogen and adds carbon dioxide as a geminal chelate bis-boryl component. The respective reactions of the two-fold HB(C6F5)2 addition to Ph-CH2CH2C[triple bond, length as m-dash]CH were studied as a geminal Lewis acid reference. Most of the products were characterized by X-ray diffraction.

| S-EPMC5369401 | biostudies-literature

Semihydrogenation of Alkynes Catalyzed by a Pyridone Borane Complex: Frustrated Lewis Pair Reactivity and Boron-Ligand Cooperation in Concert.

Project description:The metal-free cis selective hydrogenation of alkynes catalyzed by a boroxypyridine is reported. A variety of internal alkynes are hydrogenated at 80 °C under 5 bar H2 with good yields and stereoselectivity. Furthermore, the catalyst described herein enables the first metal-free semihydrogenation of terminal alkynes. Mechanistic investigations, substantiated by DFT computations, reveal that the mode of action by which the boroxypyridine activates H2 is reminiscent of the reactivity of an intramolecular frustrated Lewis pair. However, it is the change in the coordination mode of the boroxypyridine upon H2 activation that allows the dissociation of the formed pyridone borane complex and subsequent hydroboration of an alkyne. This change in the coordination mode upon bond activation is described by the term boron-ligand cooperation.

| S-EPMC7693047 | biostudies-literature

Formation of Nucleophilic Allylboranes from Molecular Hydrogen and Allenes Catalyzed by a Pyridonate Borane that Displays Frustrated Lewis Pair Reactivity.

Project description:Here we report the in situ generation of nucleophilic allylboranes from H2 and allenes mediated by a pyridonate borane that displays frustrated-Lewis-pair reactivity. Experimental and computational mechanistic investigations reveal that upon H2 activation, the covalently bound pyridonate substituent becomes a datively bound pyridone ligand. Dissociation of the formed pyridone borane complex liberates Piers borane and enables a hydroboration of the allene. The allylboranes generated in this way are reactive towards nitriles. A catalytic protocol for the formation of allylboranes from H2 and allenes and the allylation of nitriles has been devised. This catalytic reaction is a conceptually new way to use molecular H2 in organic synthesis.

| S-EPMC7814673 | biostudies-literature

Design and reactions of a carbon Lewis base/boron Lewis acid frustrated Lewis pair.

Project description:The conjugated dienamine 4 selectively adds Piers' borane [HB(C6F5)2] to give the enamine/borane system 5, which features a boratirane structure by internal enamine carbon Lewis base to boron Lewis acid interaction. Compound 5 behaves as a C/B frustrated Lewis pair and undergoes typical addition reactions to benzaldehyde, several nitriles and to sulfur dioxide.This article is part of the themed issue 'Frustrated Lewis pair chemistry'.

| S-EPMC5540844 | biostudies-literature

Bi(I)-Catalyzed Transfer-Hydrogenation with Ammonia-Borane.

Project description:A catalytic transfer-hydrogenation utilizing a well-defined Bi(I) complex as catalyst and ammonia-borane as transfer agent has been developed. This transformation represents a unique example of low-valent pnictogen catalysis cycling between oxidation states I and III, and proved useful for the hydrogenation of azoarenes and the partial reduction of nitroarenes. Interestingly, the bismuthinidene catalyst performs well in the presence of low-valent transition-metal sensitive functional groups and presents orthogonal reactivity compared to analogous phosphorus-based catalysis. Mechanistic investigations suggest the intermediacy of an elusive bismuthine species, which is proposed to be responsible for the hydrogenation and the formation of hydrogen.

| S-EPMC6728098 | biostudies-literature

Ambiphilic Frustrated Lewis Pair Exhibiting High Robustness and Reversible Water Activation: Towards the Metal-Free Hydrogenation of Carbon Dioxide.

Project description:The synthesis and structural characterization of a phenylene-bridged Frustrated Lewis Pair (FLP) having a 2,2,6,6?tetramethylpiperidine (TMP) as the Lewis base and a 9-borabicyclo[3.3.1]nonane (BBN) as the Lewis acid is reported. This FLP exhibits unique robustness towards the products of carbon dioxide hydrogenation. The compound shows reversible splitting of water, formic acid and methanol while no reaction is observed in the presence of excess formaldehyde. The molecule is incredibly robust, showing little sign of degradation after heating at 80 °C in benzene with 10 equiv. of formic acid for 24 h. The robustness of the system could be exploited in the design of metal-free catalysts for the hydrogenation of carbon dioxide.

| S-EPMC6331835 | biostudies-literature

Halogenated triphenylgallium and -indium in frustrated Lewis pair activations and hydrogenation catalysis.

Project description:The Lewis acids Ga(C6F5)3, In(C6F5)3 and Ga(C6Cl5)3 are prepared and their Lewis acidity has been probed experimentally and computationally. The species Ga(C6F5)3 and In(C6F5)3 in conjunction with phosphine donors are shown to heterolytically split H2 and catalyse the hydrogenation of an imine. In addition, frustrated Lewis pairs (FLPs) derived from Ga(C6F5)3 and In(C6F5)3 and phosphines react with diphenyldisulfide to phosphoniumgallates or indates of the form [tBu3PSPh][PhSE(C6F5)3] and [tBu3PSPh][(?-SPh)(E(C6F5)3)2] (E?=?Ga, In). The potential of the FLPs based on Ga(C6F5)3, In(C6F5)3 and Ga(C6Cl5)3 and phosphines is also shown in reactions with phenylacetylene to give pure or mixtures of the products [tBu3PH][PhCCE(C6X5)3] and R3P(Ph)C=C(H)E(C6X5)3 A number of these species are crystallographically characterized. The implications for the use of these species in FLP chemistry are considered.This article is part of the themed issue 'Frustrated Lewis pair chemistry'.

| S-EPMC5540843 | 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