Browse
Submit Data
Databases
API
Help

Dataset Information

28 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Pd-Catalyzed Allylation of Imines to Access α-CF₃-Substituted α-Amino Acid Derivatives.

ABSTRACT: We herein report a high yielding protocol for the direct α-allylation of easily accessible trifluoropyruvate-derived imines using Pd-catalysis. The reaction gives access to a variety of different α-allylated-α-CF₃-amino acids in a straightforward manner, starting from commercially available trifluoropyruvate. We also provide a proof-of-concept for an enantioselective protocol (up to er = 75:25) by using chiral phosphane ligands.

SUBMITTER: Winter M

PROVIDER: S-EPMC6887540 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Enhanced Synthetic Access to Tris-CF3-Substituted Corroles.

Project description:Separate focus on the oligomerization and oxidative cyclization steps required for the synthesis of 5,10,15-tris(trifluoromethyl)corrole revealed [bis(trifluoroacetoxy)iodo]benzene (PIFA) as a superior alternative oxidant. Under optimized conditions, the pure free-base corrole was obtained with a 6-fold increase in chemical yield and an 11-fold rise in isolated material per synthesis. The corresponding gallium(III) and manganese(III) complexes were isolated by adding the appropriate metal salt prior to corrole purification.

| S-EPMC7187640 | biostudies-literature

Additive-Free Pd-Catalyzed α-Allylation of Imine-Containing Heterocycles.

Project description:An additive-free Pd-catalyzed α-allylation of different imino-group-ontaining heterocycles is reported. The activation of α-CH pronucleophiles (pKa (DMSO) > 25) occurs without the addition of strong bases or Lewis acids using only the Pd/Xantphos catalyst system. The reaction scope has been studied for various 5- and 6-membered nitrogen-containing heterocycles (yields up to 96%). Mechanistic investigations suggest an initial allylation of the imine-N followed by a Pd-catalyzed formal aza-Claisen rearrangement.

| S-EPMC5223276 | biostudies-literature

Iridium-Catalyzed C-H Borylation of CF3-Substituted Pyridines.

Project description:Iridium-catalyzed C-H borylation of CF3-substituted pyridines is described in this paper. The boronic ester group can be installed on the α, β, or γ position of pyridine by an appropriate substitution pattern. Sterically governed regioselectivity provides convenient access to a variety of CF3-substituted pyridylboronic esters. These catalytic C-H borylation reactions were carried out neatly without the use of any solvent. Several functional groups, such as halo, ester, alkoxy, amino, etc., are compatible with this methodology. These pyridylboronic esters are amenable to column chromatography and the products were isolated in good to excellent yields. α-Borylated pyridines, although isolated in good yields, do not have a long shelf life. The boronic ester derivatives of these CF3-substituted pyridines can serve as useful precursors in the synthesis regime.

| S-EPMC8992268 | biostudies-literature

Ligand-controlled regiodivergent palladium-catalyzed decarboxylative allylation reaction to access α,α-difluoroketones.

Project description:α,α-Difluoroketones possess unique physicochemical properties that are useful for developing therapeutics and probes for chemical biology. To access the α-allyl-α,α-difluoroketone substructure, complementary palladium-catalyzed decarboxylative allylation reactions were developed to provide linear and branched α-allyl-α,α-difluoroketones. For these orthogonal processes, the fluorination pattern of the substrate enabled the ligands to dictate the regioselectivity of the transformations.

| S-EPMC4373536 | biostudies-literature

Photoinduced Trifluoromethylation with CF3Br as a Trifluoromethyl Source: Synthesis of α-CF3-Substituted Ketones.

Project description:An efficient and novel photoinduced trifluoromethylation employing CF3Br as a trifluoromethyl source is described. With commercially accessible fac-Ir(III)(ppy)3 as the catalyst, radical trifluoromethylation between O-silyl enol ether and CF3Br occurs successfully. This method provides various α-CF3-substituted ketones with a broad substrate scope in good yields under mild reaction conditions.

| S-EPMC9089747 | biostudies-literature

Regiodivergent and Diastereoselective CuH-Catalyzed Allylation of Imines with Terminal Allenes.

Project description:A copper-catalyzed, chemoselective hydrometalation process enables the use of simple allenes as allylmetal nucleophile surrogates in imine allylation reactions. By modulating the nitrogen-protecting group, either highly branched- or linear-selective addition can be achieved from the same allene. Both reactions exhibit excellent diastereoselectivity and broad functional-group tolerance. Preliminary results indicate that good enantioselectivity can also be achieved in the linear-selective reaction. Finally, a mechanistic model for the regiodivergence is proposed on the basis of density functional theory calculations.

| S-EPMC5198719 | biostudies-literature

Cross-dehydrogenative coupling enables enantioselective access to CF3-substituted all-carbon quaternary stereocenters.

Project description:A cross-dehydrogenative coupling strategy for enantioselective access to acyclic CF3-substituted all-carbon quaternary stereocenters has been established. By using catalytic DDQ with MnO2 as an inexpensive terminal oxidant, asymmetric cross coupling of racemic δ-CF3-substituted phenols with indoles proceeded smoothly, providing CF3-bearing all-carbon quaternary stereocenters with excellent chemo- and enantioselectivities. The generality of the strategy is further demonstrated by efficient construction of all-carbon quaternary stereocenters bearing other polyfluoroalkyl and perfluoroalkyl groups such as CF2Cl, C2F5, and C3F7.

| S-EPMC8157275 | biostudies-literature

Direct Access to Substituted 4-CF3 β-Lactams at the C-3 Position.

Project description:Mono- and disubstituted 4-CF3 β-lactams at the C-3 position have been obtained stereoselectively under basic conditions. A wide range of function such as alcohols, alkyls, aryls, esters, and double and triple bonds have been introduced.

| S-EPMC6691124 | biostudies-literature

Access to Chiral Diamine Derivatives through Stereoselective Cu-Catalyzed Reductive Coupling of Imines and Allenamides.

Project description:Chiral 1,2-diamino compounds are important building blocks in organic chemistry for biological applications and as asymmetric inducers in stereoselective synthesis that are challenging to prepare in a straightforward and stereoselective manner. Herein, we disclose a cost-effective and readily available Cu-catalyzed system for the reductive coupling of a chiral allenamide with N-alkyl substituted aldimines to access chiral 1,2-diamino synthons as single stereoisomers in high yields. The method shows broad reaction scope and high diastereoselectivity and can be easily scaled using standard Schlenk techniques. Mechanistic investigations by density functional theory calculations identified the mechanism and origin of stereoselectivity. In particular, the addition to the imine was shown to be reversible, which has implications toward development of catalyst-controlled stereoselective variants of the identified reductive coupling of imines and allenamides.

| S-EPMC8025098 | biostudies-literature

Enantioenriched α-substituted glutamates/pyroglutamates via enantioselective cyclopropenimine-catalyzed Michael addition of amino ester imines.

Project description:A procedure for the enantioselective synthesis of α-substituted glutamates and pyroglutamates via a cyclopropenimine-catalyzed Michael addition of amino ester imines is described. Enantioselectivities of up to 94% have been achieved, and a variety of functional groups were found to be compatible. The impact of the catalyst structure and imine substitution is discussed. Compared to other methods, this protocol allows for a broader and more enantioselective access to pyroglutamate derivatives.

| S-EPMC8381810 | biostudies-literature