Browse
Submit Data
Databases
API
Help

Dataset Information

32 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Allylic alcohols and amines by carbenoid eliminative cross-coupling using epoxides or aziridines.

ABSTRACT: α-Lithiated terminal epoxides and N-(tert-butylsulfonyl)aziridines undergo eliminative cross-coupling with α-lithio ethers, to give convergent access to allylic alcohols and allylic amines, respectively. The process can be considered as proceeding by selective strain-relieving attack (ring-opening) of the lithiated three-membered heterocycle by the lithio ether and then selective β-elimination of lithium alkoxide.

SUBMITTER: Fleming MJ

PROVIDER: S-EPMC8450947 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Preparation of stereodefined homoallylic amines from the reductive cross-coupling of allylic alcohols with imines.

Project description:Regio-, diastereo-, and enantioselective coupling reactions between imines and allylic alcohols have been developed. These coupling reactions deliver complex homoallylic amine products through a convergent C-C bond forming process that does not proceed through intermediate allylic organometallic reagents. In general, convergent coupling, by exposure of an allylic alkoxide to a preformed Ti-imine complex, occurs with allylic transposition in a predictable and stereocontrolled manner. While simple diastereoselection in these reactions is high, delivering anti-products with ?20:1 selectivity, the organometallic transformation described is compatible with a diverse range of functionality and substrates (including aliphatic and aromatic imines, allylic silanes, trisubstituted alkenes, vinyl- and aryl halides, trifluoromethyl groups, thioethers, and aromatic heterocycles). Alkene geometry of the products is a complex function of the allylic alcohol structure and is consistent with a mechanistic proposal based on syn-carbometalation followed by syn-elimination by way of a boat-like transition state geometry. Single asymmetric coupling reactions provide a means to translate the stereochemical information of the allylic alcohol to the homoallylic amine or to control diastereoselection in the coupling reactions of achiral allylic alcohols with chiral imines. Double asymmetric coupling reactions are also described that afford a unique means to control stereoselection in these complex convergent coupling processes. Finally, empirical models are proposed that are consistent with the observed stereochemical course of these coupling reactions en route to chiral homoallylic amines possessing di- or trisubstituted alkenes and anti- or syn- relative stereochemistry at the allylic and homoallylic positions.

| S-EPMC2993781 | biostudies-literature

Stereoselective cross-coupling between allylic alcohols and aldimines.

Project description:A cross-coupling reaction between an allylic alcohol and an imine is described for stereoselective allylation of aromatic and aliphatic imines. This method provides operationally simple, enantioselective access to functionalized homoallylic amines. Particularly noteworthy is direct use of a functionalized allylic alcohol as an allylating reagent without prederivatization, which obviates the use of preformed organometallic reagents or activated imine derivatives.

| S-EPMC2720054 | biostudies-literature

Allylic C-H amination cross-coupling furnishes tertiary amines by electrophilic metal catalysis.

Project description:Intermolecular cross-coupling of terminal olefins with secondary amines to form complex tertiary amines-a common motif in pharmaceuticals-remains a major challenge in chemical synthesis. Basic amine nucleophiles in nondirected, electrophilic metal-catalyzed aminations tend to bind to and thereby inhibit metal catalysts. We reasoned that an autoregulatory mechanism coupling the release of amine nucleophiles with catalyst turnover could enable functionalization without inhibiting metal-mediated heterolytic carbon-hydrogen cleavage. Here, we report a palladium(II)-catalyzed allylic carbon-hydrogen amination cross-coupling using this strategy, featuring 48 cyclic and acyclic secondary amines (10 pharmaceutically relevant cores) and 34 terminal olefins (bearing electrophilic functionality) to furnish 81 tertiary allylic amines, including 12 drug compounds and 10 complex drug derivatives, with excellent regio- and stereoselectivity (>20:1 linear:branched, >20:1 E:Z).

| S-EPMC9248036 | biostudies-literature

Complex allylation by the direct cross-coupling of imines with unactivated allylic alcohols.

Project description:Regioselective, stereoselective: The convergent coupling of allylic alcohols with imines to deliver stereodefined homoallylic amines is described (see scheme). The process proceeds with net allylic transposition without the intermediacy of allylic organometallic reagents. Two stereodefined centers and a geometrically defined di- or trisubstituted alkene are forged with high selectivity.

| S-EPMC3028933 | biostudies-literature

Simple strategy for synthesis of optically active allylic alcohols and amines by using enantioselective organocatalysis.

Project description:A simple organocatalytic one-pot protocol for the construction of optically active allylic alcohols and amines using readily available reactants and catalyst is presented. The described reaction is enabled by an enantioselective enone epoxidation/aziridination-Wharton-reaction sequence affording two highly privileged and synthetically important classes of compounds in an easy and benign way. The advantages of the described sequence include easy generation of stereogenic allylic centers, also including quaternary stereocenters, with excellent enantio- and diastereomeric-control and high product diversity. Furthermore, using monosubstituted enones as substrates, having moderate enantiomeric excess, the one-pot reaction sequence proceeds with an enantioenrichment of the products and high diastereoselectivity was achieved.

| S-EPMC2996415 | biostudies-literature

Stereochemical lability of azatitanacyclopropanes: dynamic kinetic resolution in reductive cross-coupling reactions with allylic alcohols.

Project description:Azatitanacyclopropanes (titanaziridines) are shown to be stereochemically labile under reaction conditions for reductive cross-coupling. This fundamental property has been employed to realize highly selective asymmetric coupling reactions with allylic alcohols that proceed by dynamic kinetic resolution.

| S-EPMC4012230 | biostudies-literature

Allylic cross-coupling using aromatic aldehydes as ?-alkoxyalkyl anions.

Project description:The allylic cross-coupling using aromatic aldehydes as ?-alkoxyalkyl anions is described. The synergistic palladium/copper-catalyzed reaction of aromatic aldehydes, allylic carbonates, and a silylboronate produces the corresponding homoallylic alcohol derivatives. This process involves the catalytic formation of a nucleophilic ?-silyloxybenzylcopper(I) species and the subsequent palladium-catalyzed allylic substitution.

| S-EPMC7034225 | biostudies-literature

Oxidative Amide Coupling from Functionally Diverse Alcohols and Amines Using Aerobic Copper/Nitroxyl Catalysis.

Project description:The aerobic Cu/ABNO catalyzed oxidative coupling of alcohols and amines is highlighted in the synthesis of amide bonds in diverse drug-like molecules (ABNO=9-azabicyclo[3.3.1]nonane N-oxyl). The robust method leverages the privileged reactivity of alcohols bearing electronegative hetero- atoms (O, F, N, Cl) in the ?-position. The reaction tolerates over 20 unique functional groups and is demonstrated on a 15?mmol scale under air. Steric constraints of the catalyst allow for chemoselective amidation of primary amines in the presence of secondary amines. All catalyst components are commercially available, and the reaction proceeds under mild conditions with retention of stereocenters in both reaction partners, while producing only water as a by-product.

| S-EPMC6707856 | biostudies-literature

Palladium-Catalyzed Enantioselective Intermolecular Coupling of Phenols and Allylic Alcohols.

Project description:An enantioselective intermolecular coupling of oxygen nucleophiles and allylic alcohols to give ?-aryloxycarbonyl compounds is disclosed using a chiral pyridine oxazoline-ligated palladium catalyst under mild conditions. As opposed to the formation of traditional Wacker-type products, enantioselective migratory insertion is followed by ?-hydride elimination toward the adjacent alcohol. Deuterium labeling experiments suggest a syn-migratory insertion of the alkene into the Pd-O bond. A broad scope of phenols, various allylic alcohols, and an alkyl hydroperoxide are viable coupling partners in this process.

| S-EPMC5180452 | biostudies-literature

Cascade approach to stereoselective polycyclic ether formation: epoxides as trapping agents in the transposition of allylic alcohols.

Project description:Complexity from simplicity: polycyclic ethers are synthesized by cascade reactions involving the use of epoxides as electrophilic traps in the transposition of allylic alcohols. Stereogenic centers are created by functionalizing prochiral sites under thermodynamic control, and remote stereoinduction can be achieved through the use of ketones as conduits.

| S-EPMC3857712 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

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