Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Copper-Catalyzed Enantioselective Borylative Allyl-Allyl Coupling of Allenes and Allylic gem-Dichlorides.

ABSTRACT: A catalytic asymmetric reaction between allenes, bis(pinacolato)diboron, and allylic gem-dichlorides is reported. The method involves the coupling of a catalytically generated allyl copper species with the allylic gem-dichloride and provides chiral internal 1,5-dienes featuring (Z)-configured alkenyl boronate and alkenyl chloride units with high levels of chemo-, regio-, enantio-, and diastereoselectivity. The synthetic utility of the products is demonstrated with the synthesis of a range of optically active compounds. DFT calculations reveal key noncovalent substrate-ligand interactions that account for the enantioselectivity outcome and the diastereoselective formation of the (Z)-alkenyl chloride.

SUBMITTER: Pineiro-Suarez M

PROVIDER: S-EPMC10127276 | biostudies-literature | 2023 Apr

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Copper-Catalyzed Enantioselective Borylative Allyl-Allyl Coupling of Allenes and Allylic gem-Dichlorides.

Piñeiro-Suárez Martín M Álvarez-Constantino Andrés M AM Fañanás-Mastral Martín M

ACS catalysis 20230410 8

A catalytic asymmetric reaction between allenes, bis(pinacolato)diboron, and allylic gem-dichlorides is reported. The method involves the coupling of a catalytically generated allyl copper species with the allylic gem-dichloride and provides chiral internal 1,5-dienes featuring (Z)-configured alkenyl boronate and alkenyl chloride units with high levels of chemo-, regio-, enantio-, and diastereoselectivity. The synthetic utility of the products is demonstrated with the synthe ...[more]

PMID: 37123595

Similar Datasets

Enantioselective and site-specific copper-catalyzed reductive allyl-allyl cross-coupling of allenes.

Project description:A copper-catalyzed asymmetric reductive allyl-allyl cross-coupling reaction of allenes with allylic phosphates wherein allenes were used as allylmetal surrogates has been achieved for the first time. This protocol provides an efficient and straightforward route to optically active 1,5-dienes in a highly enantioselective and site-specific fashion. Furthermore, all-carbon quaternary stereogenic centers could also be constructed with this protocol. The versatility of the products is demonstrated through a diverse array of further transformations of the enantioenriched 1,5-dienes.

| S-EPMC6369434 | biostudies-literature

Enantio- and Diastereoselective Copper-Catalyzed Allylboration of Alkynes with Allylic gem-Dichlorides.

Project description:Allylic gem-dichlorides are shown to be efficient substrates for catalytic asymmetric allylboration of alkynes. The method employs a chiral NHC-Cu catalyst capable of generating in a single step chiral skipped dienes bearing a Z-alkenyl chloride, a trisubstituted E-alkenyl boronate and a bis-allylic stereocenter with excellent levels of chemo-, regio- enantio- and diastereoselectivity. This high degree of functionalization makes these products versatile building blocks as illustrated with the synthesis of several optically active compounds. DFT calculations support the key presence of a metal cation bridge ligand-substrate interaction and account for the stereoselectivity outcome.

| S-EPMC9314970 | biostudies-literature

Pd-catalyzed enantioselective allyl-allyl cross-coupling.

Project description:The Pd-catalyzed cross-coupling of allylic carbonates and allylB(pin) is described. The regioselectivity of this reaction is sensitive to the bite angle of the ligand, with small-bite-angle ligands favoring the branched substitution product. This mode of regioselection is consistent with a reaction that operates by a 3,3' reductive elimination reaction. In the presence of appropriate chiral ligands, this reaction is rendered enantioselective and applies to both aromatic and aliphatic allylic carbonates.

| S-EPMC2925184 | biostudies-literature

Diastereo- and enantioselective anti-alkoxyallylation employing allylic gem-dicarboxylates as allyl donors via iridium-catalyzed transfer hydrogenation.

Project description:Enantioselective transfer hydrogenation of gem-dibenzoate 1e in the presence of aromatic, alpha,beta-unsaturated, or aliphatic aldehydes 2a-i mediated by isopropyl alcohol and employing a cyclometalated iridium C,O-benzoate derived from allyl acetate, 4-cyano-3-nitrobenzoic acid, and (R)-SEGPHOS delivers products of alkoxyallylation 3a-i, 4a, 4e, 4f, and 4i in good isolated yields (62-82%) with good to excellent diastereoselectivities (7:1 to 18:1 dr) and exceptional enantioselectivities (90-99% ee). This protocol provides an alternative to the use of premetalated nucleophiles in carbonyl alkoxyallylation.

| S-EPMC2824430 | biostudies-literature

Copper-Catalyzed Borylative Cross-Coupling of Allenes and Imines: Selective Three-Component Assembly of Branched Homoallyl Amines.

Project description:A copper-catalyzed three-component coupling of allenes, bis(pinacolato)diboron, and imines allows regio-, chemo-, and diastereoselective assembly of branched ?,?-substituted-?-boryl homoallylic amines, that is, products bearing versatile amino, alkenyl, and borane functionality. Alternatively, convenient oxidative workup allows access to ?-substituted-?-amino ketones. A computational study has been used to probe the stereochemical course of the cross-coupling.

| S-EPMC4736445 | biostudies-literature

Highly Enantioselective Hiyama Cross-Coupling via Rh-Catalyzed Allylic Arylation of Racemic Allyl Chlorides.

Project description:Highly enantioselective Hiyama cross-coupling reactions have been achieved through rhodium(I)-catalyzed dynamic kinetic asymmetric transformations between aryl siloxanes and cyclic racemic allyl halides. This process affords valuable enantiomerically enriched aryl-substituted cyclic allyl products and is compatible with heterocyclic allyl chloride electrophiles.

| S-EPMC7009026 | biostudies-literature

Enantioselective Copper-Catalyzed Borylative Cyclization for the Synthesis of Quinazolinones.

Project description:Quinazolinones are common substructures in molecules of medicinal importance. We report an enantioselective copper-catalyzed borylative cyclization for the assembly of privileged pyrroloquinazolinone motifs. The reaction proceeds with high enantio- and diastereocontrol, and can deliver products containing quaternary stereocenters. The utility of the products is demonstrated through further manipulations.

| S-EPMC8252434 | biostudies-literature

Enantioselective Generation of Adjacent Stereocenters in a Copper-Catalyzed Three-Component Coupling of Imines, Allenes, and Diboranes.

Project description:A highly enantio- and diastereoselective copper-catalyzed three-component coupling affords the first general synthesis of homoallylic amines bearing adjacent stereocenters from achiral starting materials. The method utilizes a commercially available NHC ligand and copper source, operates at ambient temperature, couples readily available simple imines, allenes, and diboranes, and yields high-value homoallylic amines that exhibit versatile amino, alkenyl, and boryl units.

| S-EPMC5103189 | biostudies-literature

Copper Hydride Catalyzed Enantioselective Synthesis of Axially Chiral 1,3-Disubstituted Allenes.

Project description:The general enantioselective synthesis of axially chiral disubstituted allenes from prochiral starting materials remains a long-standing challenge in organic synthesis. Here, we report an efficient enantio- and chemoselective copper hydride catalyzed semireduction of conjugated enynes to furnish 1,3-disubstituted allenes using water as the proton source. This protocol is sufficiently mild to accommodate an assortment of functional groups including keto, ester, amino, halo, and hydroxyl groups. Additionally, applications of this method for the selective synthesis of monodeuterated allenes and chiral 2,5-dihydropyrroles are described.

| S-EPMC6748664 | biostudies-literature

The allyl intermediate in regioselective and enantioselective iridium-catalyzed asymmetric allylic substitution reactions.

Project description:The isolation and structural characterization of metallacyclic allyl (2a) and crotyl (2b) iridium complexes are reported. Complexes 2a and 2b are rare examples of iriduim allyl complexes that undergo nucleophilic attack at terminal position, rather than the central position, of the allyl unit. Structures of 2a and 2b were obtained by X-ray diffraction. Nucleophilic attack was observed at the carbon that is bound to iridium trans to phosphorus through a longer Ir-C bond. However, the effect of the trans phosphine ligand on the Ir-C bond lengths was smaller than the effect of the substituent on the allyl group in 2b. The competence of complexes 2a and 2b to be intermediates in the catalytic asymmetric allylic substitutions was evaluated by studying their reactivity toward stabilized carbon and heteroatom nucleophiles and comparing the rates and selectivities to those of the catalytic reactions. The stereoselectivity and regioselectivity of stoichiometric reactions of 2b were similar to those of reactions catalyzed by the previously reported iridium catalysts, supporting their intermediacy in the catalytic reactions. On the basis of the structural data, a model is proposed for the origin of stereoselectivity in iridium-catalyzed asymmetric allylic substitution reactions.

| S-EPMC2814332 | biostudies-literature