Catalytic atroposelective synthesis

Nature Catalysis, Journal Year: 2024, Volume and Issue: 7(5), P. 483 - 498

Published: April 30, 2024

Language: Английский

---

N‐Heterocycle‐Editing to Access Fused‐BN‐Heterocycles via Ring‐Opening/C−H Borylation/Reductive C−B Bond Formation

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(10)

Published: Jan. 10, 2024

Skeletal editing of N-heterocycles has recently received considerable attention, and the introduction boron atom into heterocycles often results in positive property changes. However, direct enlargement through insertion is rarely reported literature. Here, we report a N-heterocyclic reaction combination C-H borylation, accessing fused-BN-heterocycles. The synthetic potential this chemistry was demonstrated by substrate scope late-stage diversification products.

Language: Английский

---

Atroposelective Construction of Carbon–Boron Axial Chirality through Rh-Catalyzed [2 + 2 + 2] Cycloaddition

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(7), P. 5064 - 5076

Published: March 20, 2024

Axially chiral compounds have widespread applications in many fields. While significant progress has been made for the asymmetric synthesis of atropisomers consisting C–C bonds, an efficient approach construction C–B is still lacking. Herein, we report a practical method atroposelective axially arylboron through Rh-catalyzed [2 + 2 2] cycloaddition. The reaction exhibits broad substrate scope and good functional group tolerance, thus providing protocol to access variety high yields enantiocontrol. utility these adequately demonstrated by versatile transformations into highly valuable such as phosphine ligands fluorescent molecules. Mechanistic experiments DFT calculations provided insights mechanism well origin

Language: Английский

---

Enantioselective Synthesis of Heteroatom‐Linked Non‐Biaryl Atropisomers

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(30)

Published: May 15, 2024

Atropisomers hold significant fascination, not only for their prevalence in natural compounds but also biological importance and wide-ranging applications as chiral materials, ligands, organocatalysts. While biaryl heterobiaryl atropisomers are commonly studied, the enantioselective synthesis of less abundant heteroatom-linked non-biaryl presents a formidable challenge modern organic synthesis. Unlike classical atropisomers, these molecules allow rotation around two bonds, resulting low barriers to enantiomerization through concerted bond rotations. In recent years discovery new configurationally stable rare scaffolds such aryl amines, ethers sulfones well innovative methodologies control configuration have been disclosed literature constitute topic this minireview.

Language: Английский

---

Enantioselective Synthesis of Axially Chiral Diaryl Ethers through Chiral Phosphoric Acid-Catalyzed Desymmetric Acylation with Azlactones

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(9), P. 6667 - 6673

Published: April 16, 2024

C–O axially chiral diaryl ethers play important roles in natural products and bioactive molecules, but because of the low rotational barrier strict steric hindrance requirements, catalytic asymmetric construction still remains a challenge. Herein, we devised strategy employing achiral azlactone for desymmetrization prochiral diamines under catalysis phosphoric acid. The targeted were obtained very good yields (up to 98%) high enantioselectivities >99.5:0.5 er). synthetic utility was demonstrated through large-scale reaction transformations products. Moreover, DFT calculations conducted probe origins enantioselectivity.

Language: Английский

---

Chiral Amino Acids: Evolution in Atroposelective C-H Activation

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(25), P. 5032 - 5051

Published: Jan. 1, 2024

This review covers the journey of chiral amino acids as ligands in atroposelective C–H bond activation/functionalization via transition metal catalysis.

Language: Английский

---

Recent Advances in Catalytic Desymmetrization for the Synthesis of Axially Chiral Biaryls

ChemCatChem, Journal Year: 2024, Volume and Issue: unknown

Published: June 7, 2024

Abstract Atropisomeric compounds have been discovered in pharmaceuticals and materials science, their enantioselective syntheses gained tremendous attention. Among strategies for catalytic atroposelective synthesis, desymmetrization provides robust straightforward approaches to axially chiral biaryls. Due the relative ease of substrate design compared other strategies, has emerged as a pivotal stage converting fascinating chemistry into its counterpart, despite challenges such formation achiral products by subsequent reactions long distance between reaction site stereogenic axis. This review offers comprehensive overview recent advancements using organo‐ metal catalysts, addressing solutions, aims provide insights future developments this field.

Language: Английский

---

Palladium-Catalyzed (3 + 2) Annulation of Azaborines with Vinyl Epoxides for Constructing Polycyclic Oxazaborolidines

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 25, 2025

A palladium-catalyzed (3 + 2) annulation of azaborines with vinyl epoxides has been established. By this strategy, various polycyclic oxazaborolidines structural diversity were synthesized in generally high yields (up to 99%). The can be scaled up and the further functionalized through olefin metathesis Heck reaction, which demonstrated good feasibility for downstream transformations. Moreover, catalytic asymmetric version accomplished under catalysis palladium/chiral phosphoramidite ligand, producing chiral overall enantioselectivities 98:2 er). This work not only represents first 1,2-azaborines but also offers an efficient strategy constructing benzooxazaborolidine skeletons, particularly those enantioenriched fashion.

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

---

Bifunctional Squaramide‐Catalyzed Oxidative Kinetic Resolution: Simultaneous Access to Axially Chiral Thioether and Sulfoxide

Advanced Science, Journal Year: 2024, Volume and Issue: 11(28)

Published: May 15, 2024

Abstract Axially chiral thioethers and sulfoxides emerge as two pivotal classes of ligands organocatalysts, which have remarkable features in the stereoinduction various asymmetric transformations. However, lack easy methods to access such molecules with diverse structures has hampered their broader utilization. Herein, an oxidative kinetic resolution for sulfides using a bifunctional squaramide catalyst cumene hydroperoxide terminal oxidant is established. This approach provides variety axially well bearing both axial central chirality, excellent diastereo‐ enantioselectivities. catalytic system also successfully extends benzothiophene‐based sulfides. Preliminary mechanism investigation indicates that multiple hydrogen bonding interactions between substrates play crucial role determining enantioselectivity reactivity.

Language: Английский

---