2026-10-06T05:22:48Z https://api.figshare.com/v2/oai

oai:figshare.com:article/33854126 2026-10-01T14:34:00Z category_4 category_7 category_14 category_21 category_272 category_873 category_734 category_931 category_61 portal_63 item_type_6 month_year_10_2026

Enantioselective Cross-Coupling of an Unbiased Carbon Radical Enabled by Perfluoroaryl Semicorrin Ligands Juan J. Rojas (12269232) Françoise A. Aouane (11847436) Lupita S. Ramirez (24987782) Ángel Rentería-Gómez (9306741) Yiming Zhang (444592) Marc A. Breaz (24987785) Tieze van den Elsen (24987788) Narek Azizyan (22211028) Jake B. Bailey (1365273) Milan Gembicky (2373562) Osvaldo Gutierrez (1331532) Ryan A. Shenvi (1264554) Biochemistry Medicine Molecular Biology Biotechnology Environmental Sciences not elsewhere classified Chemical Sciences not elsewhere classified Biological Sciences not elsewhere classified Information Systems not elsewhere classified Developmental Biology racemic starting material differentiation typically relies diastereomeric transition states conspicuous steric repulsion conserved nitrile group achieve high enantioselectivity semicorrin ligand class perfluoroaryl semicorrin ligands isolated carbon radicals unbiased radicals new class chiral ligands unique niche termed scarf structural properties scalemic product prove integral prochiral faces modular synthesis enantioselective cross distinctive electronic computation converge centered radical A racemic starting material can be converted into a scalemic product through the intermediacy of a carbon-centered radical if a reactant or catalyst can distinguish its prochiral faces. This differentiation typically relies on proximal Lewis basic functionality or conspicuous steric repulsion, and examples of unbiased radicals are rare. Here, we describe a modification to the semicorrin ligand class that retains its X,L-character but replaces the conserved nitrile group with fluoroarenes, which prove integral to achieve high enantioselectivity with isolated carbon radicals that lack proximal differentiating functionality. Experiment and computation converge on conformationally constraining CF···HC interactions that separate the energies of the diastereomeric transition states of C–C bond formation. Given its distinctive electronic and structural properties, dynamic CF···HC interaction network, and two-step, modular synthesis, we expect this new class of chiral ligands, termed scArF, to fill a unique niche and inspire new ligand designs. 2026-09-30T00:00:00Z Text Journal contribution 10.1021/jacs.6c15694.s002 https://figshare.com/articles/journal_contribution/Enantioselective_Cross-Coupling_of_an_Unbiased_Carbon_Radical_Enabled_by_Perfluoroaryl_Semicorrin_Ligands/33854126 CC BY-NC 4.0