New horizons for catalysis disclosed by supramolecular chemistry

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(13), P. 7681 - 7724

Published: Jan. 1, 2021

Recent advancements in supramolecular catalysis are reviewed, which show the potential of related tools when applied to organic synthesis. Such recognized as innovative instruments that can pave way alternative synthetic strategies.

Language: Английский

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Forging C−heteroatom bonds by transition-metal-catalyzed enantioselective C–H functionalization

Chem, Journal Year: 2021, Volume and Issue: 8(2), P. 384 - 413

Published: Dec. 17, 2021

Language: Английский

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Cobalt/Salox‐Catalyzed Enantioselective C−H Functionalization of Arylphosphinamides

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(25)

Published: April 6, 2022

Previous methods on CoIII -catalyzed asymmetric C-H activation rely the use of tailor-made cyclopentadienyl-ligated complexes, which require lengthy steps for preparation. Herein, we report an unprecedented enantioselective functionalization enabled by a simple cobalt/salicyloxazoline (Salox) catalysis. The chiral Salox ligands can be easily prepared in one step from salicylonitrile and amino alcohols. A broad range P-stereogenic compounds were synthesized high yields with excellent enantioselectivities (45 examples, up to 99 % yield >99 ee). isolation characterization several intermediates provided insights into generation active catalytic cobalt species, action Salox, mode stereocontrol.

Language: Английский

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Remote steric control for undirected meta -selective C–H activation of arenes

Science, Journal Year: 2022, Volume and Issue: 375(6581), P. 658 - 663

Published: Feb. 10, 2022

Regioselective functionalization of arenes remains a challenging problem in organic synthesis. Steric interactions are often used to block sites adjacent given substituent, but they do not distinguish the remaining remote sites. We report strategy based on steric control, whereby roof-like ligand protects distant para site addition ortho sites, and thereby enables selective activation meta carbon-hydrogen (C–H) bonds absence or substituents. demonstrate this concept for iridium-catalyzed -selective borylation various monosubstituted arenes, including complex drug molecules. This has potential expand toolbox C–H bond previously nondifferentiable reaction

Language: Английский

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Enantioselective desymmetrization reactions in asymmetric catalysis

Tetrahedron, Journal Year: 2022, Volume and Issue: 106-107, P. 132629 - 132629

Published: Jan. 1, 2022

Language: Английский

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Transition-Metal-Catalyzed Silylation and Borylation of C–H Bonds for the Synthesis and Functionalization of Complex Molecules

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(19), P. 11619 - 11663

Published: Sept. 26, 2023

The functionalization of C–H bonds in organic molecules containing functional groups has been one the holy grails catalysis. One synthetically important approach to diverse is catalytic silylation or borylation bonds, which enables a broad array downstream transformations afford structures. Advances both undirected and directed methods for transition-metal-catalyzed have led their rapid adoption early-, mid-, late-stage synthesis complex molecules. In this Review, we review application bioactive molecules, materials, ligands. Overall, aim provide picture state art as applied modification architectures that will spur further development these reactions.

Language: Английский

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Transition metal–catalyzed remote C─H borylation: An emerging synthetic tool

Science Advances, Journal Year: 2023, Volume and Issue: 9(16)

Published: April 21, 2023

Transition metal–catalyzed C─H bond activation and borylation is a powerful synthetic method that offers versatile transformation from organoboron compounds to virtually all other functional groups. Compared the ortho-borylation, remote remains more challenging owing inaccessibility of these bonds. Enforcing metal catalyst toward bonds needs well-judged design through proper ligand development. This review article aims summarize recent discoveries for by employment new catalyst/ligand with help steric ligand, noncovalent interactions. It has been found now takes part in total synthesis natural products shorter route. Whereas, Ir-catalyzed predominant, cobalt also started affect this field sustainable cost-effective

Language: Английский

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Synthesis of planar chiral ferrocenes via enantioselective remote C–H activation

Nature Chemistry, Journal Year: 2023, Volume and Issue: 15(6), P. 815 - 823

Published: April 17, 2023

Language: Английский

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Catalytic enantioselective nucleophilic desymmetrization of phosphonate esters

Nature Chemistry, Journal Year: 2023, Volume and Issue: 15(5), P. 714 - 721

Published: May 1, 2023

Molecules that contain a stereogenic phosphorus atom are crucial to medicine, agrochemistry and catalysis. While methods available for the selective construction of various chiral organophosphorus compounds, catalytic enantioselective approaches their synthesis far less common. Given vastness possible substituent combinations around atom, protocols preparation should also be divergent, providing facile access not only one but many classes compounds. Here we introduce strategy an enantioenriched phosphorus(V) centre can diversified enantiospecifically wide range biologically relevant The process, which involves nucleophilic substitution catalysed by superbasic bifunctional iminophosphorane catalyst, accommodate carbon substituents at phosphorus. resulting stable, yet versatile, synthetic intermediates combined with multitude medicinally O-, N- S-based nucleophiles.

Language: Английский

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Second Generation Catalytic Enantioselective Nucleophilic Desymmetrization at Phosphorus (V): Improved Generality, Efficiency and Modularity

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(18)

Published: Feb. 21, 2024

A broadly improved second generation catalytic two-phase strategy for the enantioselective synthesis of stereogenic at phosphorus (V) compounds is described. This protocol, consisting a bifunctional iminophosphorane (BIMP) catalyzed nucleophilic desymmetrization prochiral, bench stable P(V) precursors and subsequent enantiospecific substitution allows divergent access to wide range C-, N-, O- S- substituted containing from handful enantioenriched intermediates. new ureidopeptide BIMP catalyst/thiaziolidinone leaving group combination allowed far wider substrate scope increased reaction efficiency practicality over previously established protocols. The resulting intermediates could then be transformed into an even greater distinct classes by displacement remaining as well allowing further diversification downstream. Density functional theory (DFT) calculations were performed pinpoint origin enantioselectivity BIMP-catalyzed desymmetrization, rationalize how superior catalyst/leaving leads generality in our second-generation system, shed light onto observed stereochemical retention inversion pathways when performing late-stage S

Language: Английский

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