Category Ranking
98%
Total Visits
921
Avg Visit Duration
2 minutes
Citations
20
Article Abstract
Enantioselective synthesis of chiral compounds is of high interest due to their importance in organic chemistry, medicinal chemistry, life science, and materials science. Catalytic construction of chiral centers via the enantioselective carbon-carbon coupling is one of the most efficient approaches. Chiral 1,5-alkadienes are prevalent in natural and bioactive compounds. Thus, allyl-allyl coupling towards to the synthesis of chiral 1,5-alkadienes is of high interest. However, in addition to the issue of enantioselectivity, the extra challenge is the issue of regio-selectivity referring to the branched and linear products caused by the steric and electronic effect of 1,3-terminals. Herein, such challenge is addressed by a synergistic copper/palladium catalysis strategy: A three-component allylboration reaction of allenes with bis(pinacolato)diboron and allylic phosphates is developed to afford a series of optically active 1,5-alkadienes with either tertiary or quaternary carbon stereocenters. Their synthetic potentials are demonstrated, including the synthesis of (-)-protrifenbute and its derivatives.
Download full-text PDF |
Source |
|---|---|
| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC12214771 | PMC |
| http://dx.doi.org/10.1038/s41467-025-59902-z | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Non-C symmetric chiral ligand dictating allyl-allyl coupling.
Nat Commun
July 2025
Research Center for Molecular Recognition and Synthesis, Department of Chemistry, Fudan University, 220 Handan Lu, Shanghai, 200433, P. R. China.
Enantioselective synthesis of chiral compounds is of high interest due to their importance in organic chemistry, medicinal chemistry, life science, and materials science. Catalytic construction of chiral centers via the enantioselective carbon-carbon coupling is one of the most efficient approaches. Chiral 1,5-alkadienes are prevalent in natural and bioactive compounds.
View Article and Find Full Text PDFSwitching Selectivity in Borylative Allyl-Allyl Cross-Coupling through Synergistic Catalysis.
J Am Chem Soc
August 2024
Centro Singular de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS), Universidade de Santiago de Compostela, 15782 Santiago de Compostela, Spain.
A Cu/Pd-catalyzed borylative coupling of allenes with allyl carbonates is reported. Synergistic Cu/Pd catalysis enables a divergent selectivity compared to Cu catalysis and allows for the regio-, diastereo-, and enantioselective formation of synthetically versatile chiral borylated 1,5-dienes featuring two adjacent tertiary stereocenters. DFT calculations support a closed inner-sphere S2' transmetalation between the catalytic allyl copper and allyl palladium intermediates and point at the reductive elimination of the resulting bis(allyl)Pd intermediate as the regio- and diastereo-determining step.
View Article and Find Full Text PDFAllyl-Allyl Coupling Promoted by Catalyst Systems with two Palladium Atoms - A Plethora of Potentially Pericyclic Processes.
Angew Chem Int Ed Engl
July 2024
Department of Chemistry, University of California-Davis, Davis, CA 95616, USA.
Recently, Huang and co-workers reported a catalytic reaction that utilizes H as the sole reductant for a C-C coupling of allyl groups with yields up to 96 %. Here we use computational quantum chemistry to identify several key features of this reaction that provide clarity on how it proceeds. We propose the involvement of a Pd-Pd bound dimer precatalyst, demonstrate the importance of ligand π-π interactions and counterions, and identify a new, energetically viable, mechanism involving two dimerized, outer-sphere reductive elimination transition structures that determine both the rate and selectivity.
View Article and Find Full Text PDFCopper-Catalyzed Enantioselective Borylative Allyl-Allyl Coupling of Allenes and Allylic -Dichlorides.
ACS Catal
April 2023
Centro Singular de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS), Universidade de Santiago de Compostela, 15782 Santiago de Compostela, Spain.
A catalytic asymmetric reaction between allenes, bis(pinacolato)diboron, and allylic -dichlorides is reported. The method involves the coupling of a catalytically generated allyl copper species with the allylic -dichloride and provides chiral internal 1,5-dienes featuring ()-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.
View Article and Find Full Text PDFIridium-Catalyzed Chemo-, Diastereo-, and Enantioselective Allyl-Allyl Coupling: Accessing All Four Stereoisomers of (E)-1-Boryl-Substituted 1,5-Dienes by Chirality Pairing.
Angew Chem Int Ed Engl
March 2023
Department of Chemistry, Pohang University of Science and Technology (POSTECH), Pohang, 37673 (Republic of, Korea.
Here, we report a highly chemo-, diastereo-, and enantioselective allyl-allyl coupling between branched allyl alcohols and α-silyl-substituted allylboronate esters, catalyzed by a chiral iridium complex. The α-silyl-substituted allylboronate esters can be chemoselectively coupled with allyl electrophiles, affording a diverse set of enantioenriched (E)-1-boryl-substituted 1,5-dienes in good yields, with excellent stereoselectivity. By permuting the chiral iridium catalysts and the substrates, we efficiently and selectively obtained all four stereoisomers bearing two consecutive chiral centers.
View Article and Find Full Text PDF