Browse
Submit Data
Databases
API
Help

Dataset Information

22 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Stereoselective Synthesis of Tertiary Allylic Amines by Titanium-Catalyzed Hydroaminoalkylation of Alkynes with Tertiary Amines.

ABSTRACT: Intermolecular hydroaminoalkylation reactions of symmetrical and unsymmetrical alkynes with tertiary amines take place in the presence of catalytic amounts of TiBn₄ , Ph₃ C[B(C₆ F₅ )₄ ], and a sterically demanding aminopyridinato ligand precursor. The resulting products, synthetically and pharmaceutically useful tertiary β,γ-disubstituted allylic amines, are formed in convincing yields and with excellent stereoselectivity. Particularly promising for future applications is the fact that even the industrial side product trimethylamine can be used as a substrate.

SUBMITTER: Kaper T

PROVIDER: S-EPMC9303398 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Titanium-Catalyzed Intermolecular Hydroaminoalkylation of Alkenes with Tertiary Amines.

Project description:The first cationic titanium catalyst system for the intermolecular hydroaminoalkylation of alkenes with various tertiary alkylamines is presented. Corresponding reactions which involve the addition of the α-C-H bond of a tertiary amine across the C-C double bond of an alkene take place at temperatures close to room temperature with excellent regioselectivity to deliver the branched products exclusively. Interestingly, for selected amines, α-C-H bond activation occurs not only at N-methyl but also at N-methylene groups.

| S-EPMC8251730 | biostudies-literature

Ni-catalyzed hydroaminoalkylation of alkynes with amines.

Project description:Allylic amines are versatile building blocks in organic synthesis and exist in bioactive compounds, but their synthesis via hydroaminoalkylation of alkynes with amines has been a formidable challenge. Here, we report a late transition metal Ni-catalyzed hydroaminoalkylation of alkynes with N-sulfonyl amines, providing a series of allylic amines in up to 94% yield. Double ligands of N-heterocyclic carbene (IPr) and tricyclohexylphosphine (PCy3) effectively promote the reaction.

| S-EPMC8217523 | biostudies-literature

Palladium-catalyzed regio- and stereoselective ?-arylation of tertiary allylic amines: identification of potent adenylyl cyclase inhibitors.

Project description:Substituted allylic amines and their derivatives are key structural motifs of many drug molecules and natural products. A general, mild, and practical palladium-catalyzed ?-arylation of tertiary allylic amines, one of the most challenging Heck arylation substrates, has been developed. The ?-arylation products were obtained in excellent regio- and stereoselectivity. Moreover, novel and potent adenylyl cyclase inhibitors with the potential for treating neuropathic and inflammatory pain have been identified from the ?-arylation products.

| S-EPMC4692243 | biostudies-literature

Titanium-Catalyzed Hydroaminoalkylation of Ethylene.

Project description:The first examples of titanium-catalyzed hydroaminoalkylation reactions of ethylene with secondary amines are presented. The reactions can be achieved with various titanium catalysts and they do not require the use of high pressure equipment. In addition, the first solid-state structure of a titanapyrrolidine that is formed by insertion of an alkene into the Ti-C bond of a titanaaziridine is reported.

| S-EPMC7064915 | biostudies-literature

Titanium-mediated reductive cross-coupling reactions of imines with terminal alkynes: An efficient route for the synthesis of stereodefined allylic amines.

Project description:Low-valency titanium species, generated in situ by using Ti(OiPr)4/2 c-C5H9MgCl reagent, react with imines to give a titanium-imine complex that can couple with terminal alkynes to provide azatitanacyclopentenes with excellent regioselectivity. Stereodefined allylic amines are obtained in good yields after hydrolysis or iodonolysis of the corresponding azatitanacyclopentenes. When ethynylcyclopropane is used as the coupling partner to react with imines in this reaction, the initially generated allylic amine undergoes an unexpected 1,3-amino migration on silica gel during the column chromatography.

| S-EPMC3628913 | biostudies-literature

Titanium(IV)-catalyzed stereoselective synthesis of spirooxindole-1-pyrrolines.

Project description:A stereoselective cyclization between alkylidene oxindoles and 5-methoxyoxazoles has been developed using catalytic titanium(IV) chloride (as low as 5 mol %) to afford spiro[3,3'-oxindole-1-pyrrolines] in excellent yield (up to 99%) and diastereoselectivity (up to 99:1). Using a chiral scandium(III)-indapybox/BArF complex affords enantioenriched spirooxindole-1-pyrrolines where a ligand-induced reversal of diastereoselectivity is observed. This methodology is further demonstrated for the synthesis of pyrrolines from malonate alkylidene and coumarin derivatives.

| S-EPMC4275133 | biostudies-other

Scandium-catalysed intermolecular hydroaminoalkylation of olefins with aliphatic tertiary amines.

Project description:A homoleptic scandium trialkyl complex in combination with a borate compound served as an excellent catalyst for the C-H addition of aliphatic tertiary amines to olefins. This highly regiospecific, 100% atom efficient C-H bond alkylation reaction was applicable to a wide variety of tertiary amines and olefins, including functionalised styrenes and unactivated α-olefins. This work represents the first example of rare-earth catalysed olefin hydroaminoalkylation and also the first example of catalytic C-H addition of aliphatic tertiary amines to olefins with any catalyst.

| S-EPMC5356020 | biostudies-literature

Silver-Catalyzed Stereoselective Aminosulfonylation of Alkynes.

Project description:A silver-catalyzed intermolecular aminosulfonylation of terminal alkynes with sodium sulfinates and TMSN3 is reported. This three-component reaction proceeds through sequential hydroazidation of the terminal alkyne and addition of a sulfonyl radical to the resultant vinyl azide. The method enables the stereoselective synthesis of a wide range of ?-sulfonyl enamines without electron-withdrawing groups on the nitrogen atom. These enamines are found to be suitable for a variety of further transformations.

| S-EPMC5655761 | biostudies-literature

Stereoselective cobalt-catalyzed halofluoroalkylation of alkynes.

Project description:Stereoselective additions of highly functionalized reagents to available unsaturated hydrocarbons are an attractive synthetic tool due to their high atom economy, modularity, and rapid generation of complexity. We report efficient cobalt-catalyzed (E)-halofluoroalkylations of alkynes/alkenes that enable the construction of densely functionalized, stereodefined fluorinated hydrocarbons. The mild conditions (2 mol% cat., 20 °C, acetone/water, 3 h) tolerate various functional groups, i.e. halides, alcohols, aldehydes, nitriles, esters, and heteroarenes. This reaction is the first example of a highly stereoselective cobalt-catalyzed halo-fluoroalkylation. Unlike related cobalt-catalyzed reductive couplings and Heck-type reactions, it operates via a radical chain mechanism involving terminal halogen atom transfer which obviates the need for a stoichiometric sacrificial reductant.

| S-EPMC5892352 | biostudies-literature

Intermolecular Hydroaminoalkylation of Alkynes.

Project description:Intermolecular hydroaminoalkylation reactions of alkynes with secondary amines, which selectively give access to allylic amines with E configuration of the alkene unit, are achieved in the presence of titanium catalysts. Successful reactions of symmetrically substituted diaryl- and dialkylalkynes as well as a terminal alkyne take place with N-benzylanilines, N-alkylanilines, and N-alkylbenzylamines.

| S-EPMC8248392 | 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