Equivalent Atrop- and Positional Isomerism in Styrene Derivatives Prepared by Enantioselective 1,3-Diarylation
Year: 2025
Type: article
Abstract: Isomerism, the ability of a single set of atoms within a molecule to exist in different three-dimensional spatial arrangements connecting through distinct bonding networks, gives rise to distinct physical properties from a common set of atomic building blocks. While different forms of isomerism are now well appreciated, a rare phenomenon is the coexistence of multiple equivalent forms of isomerism within a given pair of molecules. Here, we report that a simple combination of palladium and amino acid co-catalysts converts ortho-alkenyl benzaldehydes into substituted styrenes possessing equivalent atrop- and positional isomerism. Mechanistically, the reaction proceeds through successive Mizoroki–Heck arylation promoted by the amino acid co-catalyst. DFT calculations show that the atroposelectivity arises from stereoselective β-H elimination in the second arylation cycle, whereas the formation of (Z)-products with constrained rotation about the chiral axis is driven by the thermodynamic stability of the (Z)-isomer.
DOI: 10.1021/jacs.5c10118
Authors: Amit Kumar Simlandy, Yiyao Hu, Turki M. Alturaifi, Wen-Ji He, Madeline J. Fitzgerald, Peng Liu, Keary M. Engle
Institutions: Scripps Research Institute, University of Pittsburgh
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
Funders: National Science Foundation, Indian Institute of Science, University of Pittsburgh, National Institutes of Health, University of California, San Diego, Center for Research Computing, University of Pittsburgh, National Institute of General Medical Sciences, Office of Advanced Cyberinfrastructure, Division of Chemistry
Awards: G1309160875, G1370689234, G1453181110, G1555197637, G1787346651, Track 4: Advanced CI Coordination Ecosystem: Monitoring and Measurement Services, G2592393619, G3025648356, G3384453195, G338811424, G34258105, G3562386289, Track 1: ACCESS Resource Allocations Marketplace and Platform Services (RAMPS), G4010157413, G4275568664, ACO: An Open CI Ecosystem to Advance Scientific Discovery (OpenCI), G5070620238, Track 3: COre National Ecosystem for CyberinfrasTructure (CONECT), G5156331529, G5367127336, G5464919783, MRI: Acquisition of Cutting-Edge GPU and MPI Nodes for the Interdisciplinary Pitt Center for Research Computing, CAREER: Catalytic Activation of Alkenyl C-H Bonds, G7218924412, G7401800883, G7526614437, G7916508619, Track 2: Customized Multi-tier Assistance, Training, and Computational Help (MATCH) for End User ACCESS to CI, G8499740153, REU Site: Scripps Structure and Function Summer Institute (SFSI), G8994211811, G9000044859, G9000102609
OpenAlex ID: W4415455883