Ether-Directed Enantioselective C(sp²)–H Borylation for the Synthesis of Axially Chiral Biaryls

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: April 9, 2025

We report an ether-directed enantioselective C(sp2)-H borylation catalyzed by a chiral bidentate boryl ligand (CBL)/iridium system for constructing axially biaryls. This method delivered diverse biaryls with good to high enantioselectivities, accommodating varied electronic and steric substituents on the aryl rings. Gram-scale synthesis downstream transformations of C-B bond underscored its practicality.

Language: Английский

Synthesis of Axially Chiral Compounds via Transition Metal-Catalyzed Atroposelective C–H Functionalization

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: April 14, 2025

ConspectusAxially chiral skeletons are prevalent in natural products and biologically important compounds, they widely utilized as privileged scaffolds enantioselective catalysis. Consequently, the catalytic atroposelective synthesis of enantiopure atropisomers has garnered considerable attention. A variety synthetic strategies involving metal catalysis or organocatalysis have been developed. Among these elegant approaches, transition metal-catalyzed C-H activation emerged an atom- step-economical strategy to streamline construction axially compounds recent years.In this Account, we discuss our efforts different types including biaryls, atropisomeric styrenes, C-N atropisomers, via strategies. To end, developed several transient directing group (cTDG) using Pd(OAc)2 tert-leucine (Tle), well systems Pd(II)/chiral phosphoric acid (CPA), Pd(II)/l-pyroglutamic (pGlu), Pd(0)/norbornene cooperative with a biimidazoline (BiIM) ligand, Co(II)/salicyloxazoline (Salox).At outset, successfully applied cTDG access biaryl aldehydes through Pd-catalyzed olefination, alkynylation, allylation, naphthylation, alkylation. The efficacy methods demonstrated aldehyde catalysts products, such TAN-1085, (+)-isochizandrin, (+)-steganone. facilitate diverse functionalities, novel Pd(II)/CPA system, which enables preparation various quinolines, biaryl-2-amines, biaryls bearing chalcogenoether units high enantioselectivities. system also allows for more challenging conjugated diene-based styrenes.Nonbiaryl styrenes anilides, present challenges due their conformational instability higher degree rotational freedom compared counterparts. We addressed achieved highly efficient anilides Pd(II)/pGlu Pd(0)/norbornene/BiIM In addition palladium catalysis, cobalt(II)/Salox vicinal C-C stereogenic axes, remote distinct diaxes, calix[4]arenes featuring both inherent axial chirality. anticipate that will find broad applications synthetically useful compounds.

Language: Английский

Palladium-Catalyzed Synthesis of 2-(1-Isochromen-3-yl)acetalde-hydes via Carboxyl-Directed C(sp²)—H Alkylation/Annulation

Chinese Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 44(11), P. 3556 - 3556

Published: Jan. 1, 2024

Language: Английский