Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Manganese(I)-Catalyzed H-P Bond Activation via Metal-Ligand Cooperation.

ABSTRACT: Here we report that chiral Mn(I) complexes are capable of H-P bond activation. This activation mode enables a general method for the hydrophosphination of internal and terminal α,β-unsaturated nitriles. Metal-ligand cooperation, a strategy previously not considered for catalytic H-P bond activation, is at the base of the mechanistic action of the Mn(I)-based catalyst. Our computational studies support a stepwise mechanism for the hydrophosphination and provide insight into the origin of the enantioselectivity.

SUBMITTER: Perez JM

PROVIDER: S-EPMC8662621 | biostudies-literature | 2021 Dec

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Manganese(I)-Catalyzed H-P Bond Activation via Metal-Ligand Cooperation.

Pérez Juana M JM Postolache Roxana R Castiñeira Reis Marta M Sinnema Esther G EG Vargová Denisa D de Vries Folkert F Otten Edwin E Ge Luo L Harutyunyan Syuzanna R SR

Journal of the American Chemical Society 20211119 48

Here we report that chiral Mn(I) complexes are capable of H-P bond activation. This activation mode enables a general method for the hydrophosphination of internal and terminal α,β-unsaturated nitriles. Metal-ligand cooperation, a strategy previously not considered for catalytic H-P bond activation, is at the base of the mechanistic action of the Mn(I)-based catalyst. Our computational studies support a stepwise mechanism for the hydrophosphination and provide insight into the origin of the enan ...[more]

PMID: 34797634

Similar Datasets

Manganese-Pincer-Catalyzed Nitrile Hydration, α-Deuteration, and α-Deuterated Amide Formation via Metal Ligand Cooperation.

Project description:A simple and efficient system for the hydration and α-deuteration of nitriles to form amides, α-deuterated nitriles, and α-deuterated amides catalyzed by a single pincer complex of the earth-abundant manganese capable of metal-ligand cooperation is reported. The reaction is selective and tolerates a wide range of functional groups, giving the corresponding amides in moderate to good yields. Changing the solvent from tert-butanol to toluene and using D2O results in formation of α-deuterated nitriles in high selectivity. Moreover, α-deuterated amides can be obtained in one step directly from nitriles and D2O in THF. Preliminary mechanistic studies suggest the transformations contributing toward activation of the nitriles via a metal-ligand cooperative pathway, generating the manganese ketimido and enamido pincer complexes as the key intermediates for further transformations.

| S-EPMC8383274 | biostudies-literature

Highly Selective, Efficient Deoxygenative Hydrogenation of Amides Catalyzed by a Manganese Pincer Complex via Metal-Ligand Cooperation.

Project description:Deoxygenative hydrogenation of amides to amines homogeneously catalyzed by a complex of an Earth-abundant metal is presented. This manganese-catalyzed reaction features high efficiency and selectivity. A plausible reaction mechanism, involving metal-ligand cooperation of the manganese pincer complex, is proposed based on NMR studies and relevant stoichiometric reactions.

| S-EPMC6503579 | biostudies-literature

Metal-Ligand Cooperation Facilitates Bond Activation and Catalytic Hydrogenation with Zinc Pincer Complexes.

Project description:A series of PNP zinc pincer complexes capable of bond activation via aromatization/dearomatization metal-ligand cooperation (MLC) were prepared and characterized. Reversible heterolytic N-H and H-H bond activation by MLC is shown, in which hemilability of the phosphorus linkers plays a key role. Utilizing this zinc pincer system, base-free catalytic hydrogenation of imines and ketones is demonstrated. A detailed mechanistic study supported by computation implicates the key role of MLC in facilitating effective catalysis. This approach offers a new strategy for (de)hydrogenation and other catalytic transformations mediated by zinc and other main group metals.

| S-EPMC7453403 | biostudies-literature

Manganese-catalyzed allylation <i>via</i> sequential C-H and C-C/C-Het bond activation.

Project description:Manganese-catalyzed sequential C-H and C-C/C-Het bond activation to synthesize allylic alcohols, allylated arenes, functionalized cyclopentenes and skipped dienes is reported. This protocol can be readily scaled up and various coupling partners are applied in manganese catalysis for the first time. Moreover, manganese-catalyzed alkenyl C(sp2)-H activation is also shown. Complimentary to the standard solution-based protocols, these reactions also proceed efficiently under neat conditions, which is unprecedented for abundant metal catalyzed C-H activation reactions.

| S-EPMC5416941 | biostudies-literature

Copper Catalyzed C(sp<sup>3</sup>)-H Bond Alkylation via Photoinduced Ligand-to-Metal Charge Transfer.

Project description:Utilizing catalytic CuCl2 we report the functionalization of numerous feedstock chemicals via the coupling of unactivated C(sp3)-H bonds with electron-deficient olefins. The active cuprate catalyst undergoes Ligand-to-Metal Charge Transfer (LMCT) to enable the generation of a chlorine radical which acts as a powerful hydrogen atom transfer reagent capable of abstracting strong electron-rich C(sp3)-H bonds. Of note is that the chlorocuprate catalyst is an exceedingly mild oxidant (0.5 V vs SCE) and that a proposed protodemetalation mechanism offers a broad scope of electron-deficient olefins, offering high diastereoselectivity in the case of endocyclic alkenes. The coupling of chlorine radical generation with Cu reduction through LMCT enables the generation of a highly active HAT reagent in an operationally simple and atom economical protocol.

| S-EPMC8608032 | biostudies-literature

Understanding Precatalyst Activation and Speciation in Manganese-Catalyzed C-H Bond Functionalization Reactions.

Project description:An investigation into species formed following precatalyst activation in Mn-catalyzed C-H bond functionalization reactions is reported. Time-resolved infrared spectroscopy demonstrates that light-induced CO dissociation from precatalysts [Mn(C^N)(CO)4] (C^N = cyclometalated 2-phenylpyridine (1a), cyclometalated 1,1-bis(4-methoxyphenyl)methanimine (1b)) in a toluene solution of 2-phenylpyridine (2a) or 1,1-bis(4-methoxyphenyl)methanimine (2b) results in the initial formation of solvent complexes fac-[Mn(C^N)(CO)3(toluene)]. Subsequent solvent substitution on a nanosecond time scale then yields fac-[Mn(C^N)(CO)3(κ1-(N)-2a)] and fac-[Mn(C^N)(CO)3(κ1-(N)-2b)], respectively. When the experiments are performed in the presence of phenylacetylene, the initial formation of fac-[Mn(C^N)(CO)3(toluene)] is followed by a competitive substitution reaction to give fac-[Mn(C^N)(CO)3(2)] and fac-[Mn(C^N)(CO)3(η2-PhC2H)]. The fate of the reaction mixture depends on the nature of the nitrogen-containing substrate used. In the case of 2-phenylpyridine, migratory insertion of the alkyne into the Mn-C bond occurs, and fac-[Mn(C^N)(CO)3(κ1-(N)-2a)] remains unchanged. In contrast, when 2b is used, substitution of the η2-bound phenylacetylene by 2b occurs on a microsecond time scale, and fac-[Mn(C^N)(CO)3(κ1-(N)-2b)] is the sole product from the reaction. Calculations with density functional theory indicate that this difference in behavior may be correlated with the different affinities of 2a and 2b for the manganese. This study therefore demonstrates that speciation immediately following precatalyst activation is a kinetically controlled event. The most dominant species in the reaction mixture (the solvent) initially binds to the metal. The subsequent substitution of the metal-bound solvent is also kinetically controlled (on a ns time scale) prior to the thermodynamic distribution of products being obtained.

| S-EPMC10369674 | biostudies-literature

Tuning Ruthenium Carbene Complexes for Selective P-H Activation through Metal-Ligand Cooperation.

Project description:The use of iminophosphoryl-tethered ruthenium carbene complexes to activate secondary phosphine P-H bonds is reported. Complexes of type [(p-cymene)-RuC(SO2 Ph)(PPh2 NR)] (with R = SiMe3 or 4-C6 H4 -NO2 ) were found to exhibit different reactivities depending on the electronics of the applied phosphine and the substituent at the iminophosphoryl moiety. Hence, the electron-rich silyl-substituted complex undergoes cyclometallation or shift of the imine moiety after cooperative activation of the P-H bond across the M=C linkage, depending on the electronics of the applied phosphine. Deuteration experiments and computational studies proved that cyclometallation is initiated by the activation process at the M=C bond and triggered by the high electron density at the metal in the phosphido intermediates. Consistently, replacement of the trimethylsilyl (TMS) group by the electron-withdrawing 4-nitrophenyl substituent allowed the selective cooperative P-H activation to form stable activation products.

| S-EPMC9299219 | biostudies-literature

New access to H-phosphonates via metal-catalyzed phosphorus-oxygen bond formation.

Project description:A novel approach to H-phosphonates from hypophosphorous acid using a transfer hydrogenation process was developed. This method is atom-economical, environmentally friendly, catalytic, and efficient, leading easily to H-phosphonate monoesters or ammonium salt in moderate to good yields.

| S-EPMC2084078 | biostudies-literature

Iodine-Iodine Cooperation Enables Metal-Free C-N Bond-Forming Electrocatalysis via Isolable Iodanyl Radicals.

Project description:Small molecule redox mediators convey interfacial electron transfer events into bulk solution and can enable diverse substrate activation mechanisms in synthetic electrocatalysis. Here, we report that 1,2-diiodo-4,5-dimethoxybenzene is an efficient electrocatalyst for C-H/E-H coupling that operates at as low as 0.5 mol % catalyst loading. Spectroscopic, crystallographic, and computational results indicate a critical role for a three-electron I-I bonding interaction in stabilizing an iodanyl radical intermediate (i.e., formally I(II) species). As a result, the optimized catalyst operates at more than 100 mV lower potential than the related monoiodide catalyst 4-iodoanisole, which results in improved product yield, higher Faradaic efficiency, and expanded substrate scope. The isolated iodanyl radical is chemically competent in C-N bond formation. These results represent the first examples of substrate functionalization at a well-defined I(II) derivative and bona fide iodanyl radical catalysis and demonstrate one-electron pathways as a mechanistic alternative to canonical two-electron hypervalent iodine mechanisms. The observation establishes I-I redox cooperation as a new design concept for the development of metal-free redox mediators.

| S-EPMC10251780 | biostudies-literature

Ligand-Metal Cooperation Enables Net Ring-Opening C-C Activation / Difunctionalization of Cyclopropyl Ketones.

Project description:Reactions that cleave C-C bonds and enable functionalization at both carbon sites are powerful strategic tools in synthetic chemistry. Stereodefined cyclopropyl ketones have become readily available and would be an ideal source of 3-carbon fragments, but general approaches to net C-C activation / difunctionalization are unknown. Herein we demonstrate the cross-coupling of cyclopropyl ketones with organozinc reagents and chlorotrimethylsilane to form 1,3-difunctionalized, ring-opened products. A combination of experimental and theoretical studies rule out more established mechanisms and shed light on how cooperation between the redox-active terpyridine (tpy) ligand and the nickel atom enables the C-C bond activation step. The reduced (tpy•-)NiI species activates the C-C bond via a concerted asynchronous ring-opening transition state. The resulting alkylnickel(II) intermediate can then be engaged by aryl-, alkenyl-, and alkylzinc reagents to furnish cross-coupled products. This allows quick access to products that are difficult to make by conjugate addition methods, such as β-allylated and β -benzylated enol ethers. The utility of this approach is demonstrated in the synthesis of a key (±)-taiwaniaquinol B intermediate and the total synthesis of prostaglandin D1.

| S-EPMC11463996 | 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