Browse
Submit Data
Databases
API
Help

Dataset Information

16 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Sulfone Group as a Versatile and Removable Directing Group for Asymmetric Transfer Hydrogenation of Ketones.

ABSTRACT: The sulfone functional group has a strong capacity to direct the asymmetric transfer hydrogenation (ATH) of ketones in the presence of [(arene)Ru(TsDPEN)H] complexes by adopting a position distal to the ?6 -arene ring. This preference provides a means for the prediction of the sense of asymmetric reduction. The sulfone group also facilitates the formation of a range of reduction substrates, and its ready removal provides a route to enantiomerically enriched alcohols that would otherwise be extremely difficult to prepare by direct ATH of the corresponding ketones.

SUBMITTER: Vyas VK

PROVIDER: S-EPMC7496949 | biostudies-literature | 2020 May

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Sulfone Group as a Versatile and Removable Directing Group for Asymmetric Transfer Hydrogenation of Ketones.

Vyas Vijyesh K VK Clarkson Guy J GJ Wills Martin M

Angewandte Chemie (International ed. in English) 20200701 34

The sulfone functional group has a strong capacity to direct the asymmetric transfer hydrogenation (ATH) of ketones in the presence of [(arene)Ru(TsDPEN)H] complexes by adopting a position distal to the η<sup>6</sup> -arene ring. This preference provides a means for the prediction of the sense of asymmetric reduction. The sulfone group also facilitates the formation of a range of reduction substrates, and its ready removal provides a route to enantiomerically enriched alcohols that would otherwi ...[more]

PMID: 32463162

Similar Datasets

trans-Diastereoselective Ru(II)-Catalyzed Asymmetric Transfer Hydrogenation of α-Acetamido Benzocyclic Ketones via Dynamic Kinetic Resolution.

Project description:A highly efficient enantio- and diastereoselective catalyzed asymmetric transfer hydrogenation via dynamic kinetic resolution (DKR-ATH) of α,β-dehydro-α-acetamido and α-acetamido benzocyclic ketones to ent- trans-β-amido alcohols is disclosed employing a new ansa-Ru(II) complex of an enantiomerically pure syn- N, N-ligand, i.e. ent- syn-ULTAM-(CH2)3Ph. DFT calculations of the transition state structures revealed an atypical two-pronged substrate attractive stabilization engaging the commonly encountered CH/π electrostatic interaction and a new additional O═S═O···HNAc H-bond hence favoring the trans-configured products.

| S-EPMC6750876 | biostudies-literature

Palladium-Catalyzed Decarboxylative ortho-Acylation of Anilines with Carbamate as a Removable Directing Group.

Project description:An efficient palladium-catalyzed decarboxylative ortho-acylation of anilines with α-oxocarboxylic acids has been realized by using carbamate as a directing group (DG). The reaction proceeds smoothly with high regioselectivity to afford diverse acylation products of aniline derivatives in moderate to good yields under mild conditions. This transformation exhibits broad substrate scope and highly functional group tolerance. In addition, the employed DG can be easily removed to give the corresponding 2-amino aromatic ketones. Importantly, several transformations of the synthesized ortho-acylated anilines into several synthetically valuable products have been demonstrated for their utilities.

| S-EPMC6641432 | biostudies-literature

Copper-catalyzed asymmetric hydrogenation of 2-substituted ketones via dynamic kinetic resolution.

Project description:A new class of tunable heterophosphole dimeric ligands have been designed and synthesized. These ligands have enabled the first examples of Cu-catalyzed hydrogenation of 2-substituted-1-tetralones and related heteroaryl ketones via dynamic kinetic resolution, simultaneously creating two contiguous stereogenic centers with up to >99?:?1 dr and 98?:?2 er. The ligand-Cu complexes were isolated and characterized by single crystal X-ray, and DFT calculations revealed a novel heteroligated dimeric copper hydride transition state.

| S-EPMC5958347 | biostudies-literature

A Simple and Versatile Amide Directing Group for C-H Functionalizations.

Project description:Achieving selective C-H activation at a single and strategic site in the presence of multiple C-H bonds can provide a powerful and generally useful retrosynthetic disconnection. In this context, a directing group serves as a compass to guide the transition metal to C-H bonds by using distance and geometry as powerful recognition parameters to distinguish between proximal and distal C-H bonds. However, the installation and removal of directing groups is a practical drawback. To improve the utility of this approach, one can seek solutions in three directions: 1) Simplifying the directing group, 2) using common functional groups or protecting groups as directing groups, and 3) attaching the directing group to substrates via a transient covalent bond to render the directing group catalytic. This Review describes the rational development of an extremely simple and yet broadly applicable directing group for Pd(II) , Rh(III) , and Ru(II) catalysts, namely the N-methoxy amide (CONHOMe) moiety. Through collective efforts in the community, a wide range of C-H activation transformations using this type of simple directing group have been developed.

| S-EPMC5518755 | biostudies-other

Enantioselective Total Synthesis of (-)-Finerenone Using Asymmetric Transfer Hydrogenation.

Project description:(-)-Finerenone is a nonsteroidal mineralocorticoid receptor antagonist currently in phase III clinical trials for the treatment of chronic kidney disease in type 2 diabetes. It contains an unusual dihydronaphthyridine core. We report a 6-step synthesis of (-)-finerenone, which features an enantioselective partial transfer hydrogenation of a naphthyridine using a chiral phosphoric acid catalyst with a Hantzsch ester. The process is complicated by the fact that the naphthyridine exists as a mixture of two atropisomers that react at different rates and with different selectivities. The intrinsic kinetic resolution was converted into a kinetic dynamic resolution at elevated temperature, which enabled us to obtain (-)-finerenone in both high yield and high enantioselectivity. DFT calculations have revealed the origin of selectivity.

| S-EPMC7839499 | biostudies-literature

4-Aminobenzotriazole (ABTA) as a Removable Directing Group for Palladium-Catalyzed Aerobic Oxidative C-H Olefination.

Project description:4-Aminobenzotriazole (ABTA) was applied as an effective removable directing group (DG) in Pd-catalyzed C-H activation for the first time. Compared with the widely applied pyridine and quinoline analogs, ABTA showed significantly improved reactivity, achieving aerobic oxidative C-H olefination in excellent yields (up to 95% vs <50% with other reported DGs under identical conditions). Using this new strategy, macrocyclization was achieved to give cyclic peptides in good yields with easy ABTA removal under mild conditions, highlighting the promising potential of this new DG.

| S-EPMC10264207 | biostudies-literature

Aminotriazole Mn(I) Complexes as Effective Catalysts for Transfer Hydrogenation of Ketones.

Project description:A catalytic system based on complexes comprising abundant and cheap manganese together with readily available aminotriazole ligands is reported. The new Mn(I) complexes are catalytically competent in transfer hydrogenation of ketones with 2-propanol as hydrogen source. The reaction proceeds under mild conditions at 80 °C for 20 h with 3 % of catalyst loading using either KO t Bu or NaOH as base. Good to excellent yields were obtained for a wide substrate scope with broad functional group tolerance. The obtained results by varying the substitution pattern of the ligand are consistent with an out-sphere mechanism for the H-transfer.

| S-EPMC6220868 | biostudies-literature

Walphos versus Biferrocene-Based Walphos Analogues in the Asymmetric Hydrogenation of Alkenes and Ketones.

Project description:Two representative Walphos analogues with an achiral 2,2?-biferrocenediyl backbone were synthesized. These diphosphine ligands were tested in the rhodium-catalyzed asymmetric hydrogenation of several alkenes and in the ruthenium-catalyzed hydrogenation of two ketones. The results were compared with those previously obtained on using biferrocene ligands with a C2-symmetric 2,2?-biferrocenediyl backbone as well as with those obtained with Walphos ligands. The application of one newly synthesized ligand in the hydrogenation of 2-methylcinnamic acid gave (R)-2-methyl-3-phenylpropanoic acid with full conversion and with 92% ee. The same ligand was used to transform 2,4-pentanedione quantitatively and diastereoselectively into (S,S)-2,4-pentanediol with 98% ee.

| S-EPMC4006446 | biostudies-literature

Easy To Synthesize, Robust Organo-osmium Asymmetric Transfer Hydrogenation Catalysts.

Project description:Asymmetric transfer hydrogenation (ATH) is an important process in organic synthesis for which the Noyori-type Ru(II) catalysts [(arene)Ru(Tsdiamine)] are now well established and widely used. We now demonstrate for the first time the catalytic activity of the osmium analogues. X-ray crystal structures of the 16-electron Os(II) catalysts are almost identical to those of Ru(II). Intriguingly the precursor complex was isolated as a dichlorido complex with a monodentate amine ligand. The Os(II) catalysts are readily synthesised (within 1 h) and exhibit excellent enantioselectivity in ATH reactions of ketones.

| S-EPMC4832837 | biostudies-literature

A New Mechanism of Metal-Ligand Cooperative Catalysis in Transfer Hydrogenation of Ketones.

Project description:We report iridium catalysts IrCl(η5-Cp*)(κ2-(2-pyridyl)CH2NSO2C6H4X) (1-Me, X = CH3 and 1-F, X = F) for transfer hydrogenation of ketones with 2-propanol that operate by a previously unseen metal-ligand cooperative mechanism. Under the reaction conditions, complexes 1 (1-Me and 1-F) derivatize to a series of catalytic intermediates: Ir(η5-Cp*)(κ2-(C5H4N)CHNSO2Ar) (2), IrH(η5Cp*)(κ2-(2-pyridyl)CH2NSO2Ar) (3), and Ir(η5-Cp*)(κ3-(2-pyridyl)CH2NSO2Ar) (4). The structures of 1-Me and 4-Me were established by single-crystal X-ray diffraction. A rate-determining, concerted hydrogen transfer step (2 + R2CHOH ⇄ 3 + R2CO) is suggested by kinetic isotope effects, Eyring parameters (ΔH ≠ = 29.1(8) kcal mol-1 and ΔS ≠ = -17(19) eu), proton-hydride fidelity, and DFT calculations. According to DFT, a nine-membered cyclic transition state is stabilized by an alcohol molecule that serves as a proton shuttle.

| S-EPMC7224354 | 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