Gold-Catalyzed Synthesis of Small Rings

Chemical Reviews, Journal Year: 2020, Volume and Issue: 121(14), P. 8613 - 8684

Published: Nov. 2, 2020

Three- and four-membered rings, widespread motifs in nature medicinal chemistry, have fascinated chemists ever since their discovery. However, due to energetic considerations, small rings are often difficult assemble. In this regard, homogeneous gold catalysis has emerged as a powerful tool construct these highly strained carbocycles. This review aims provide comprehensive summary of all the major advances discoveries made gold-catalyzed synthesis cyclopropanes, cyclopropenes, cyclobutanes, cyclobutenes, corresponding heterocyclic or heterosubstituted analogs.

Language: Английский

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1,2-Migrations onto Gold Carbene Centers

Chemical Reviews, Journal Year: 2020, Volume and Issue: 121(14), P. 8948 - 8978

Published: Oct. 7, 2020

Gold carbenes are highly active intermediates in homogeneous gold catalysis, enabling a large array of transformations such as C–H/X–H insertions, cyclopropanations, and 1,2-migrations. Unlike insertions 1,2-migrations onto carbene centers seem to be attracting less attention. There has been no comprehensive review focusing on this topic, even though chemistry become powerful tool for the rapid simple construction molecular complexity. This provides critical information centers, drawing preliminary conclusion migratory aptitude various groups. The is divided into several parts according kind precursors.

Language: Английский

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Recent Developments in Enantioselective Transition Metal Catalysis Featuring Attractive Noncovalent Interactions between Ligand and Substrate

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(18), P. 10672 - 10714

Published: Aug. 14, 2020

Enantioselective transition metal catalysis is an area very much at the forefront of contemporary synthetic research. The development processes that enable efficient synthesis enantiopure compounds unquestionable importance to chemists working within many diverse fields central science. Traditional approaches solving this challenge have typically relied on leveraging repulsive steric interactions between chiral ligands and substrates in order raise energy one diastereomeric states over other. By contrast, Review examines alternative tactic which a set attractive noncovalent operating are used control enantioselectivity. Examples where creative approach has been successfully applied render fundamental enantioselective presented discussed. In cases examined, ligand scaffold carefully designed accommodate these interactions, while others, critical was only elucidated subsequent computational mechanistic studies. Through exploration discussion recent reports encompassing wide range reaction classes, we hope inspire continue develop asymmetric transformations based powerful concept.

Language: Английский

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Dinuclear gold catalysis

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 50(3), P. 1874 - 1912

Published: Dec. 14, 2020

Gold chemistry has developed extensively in the past decade, and a dozen good reviews have been presented discussing this progress. Few however paid close attention to progress organic synthesis of dinuclear gold-catalysis. A gold catalyst is defined here as complex with two centers linked by bidentate ligand. With theoretical analysis some representative studies recent years, comprehensive review highlights particular properties gold-complexes, especially aurophilic interactions, systematically summarizes achievements gold-catalyzed coupling reactions, asymmetric catalysis, photocatalysis, where catalysts tend show greater advantage than mononuclear catalysts.

Language: Английский

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Au-Catalyzed Intermolecular [2+2] Cycloadditions between Chloroalkynes and Unactivated Alkenes

Journal of the American Chemical Society, Journal Year: 2018, Volume and Issue: 140(17), P. 5860 - 5865

Published: April 4, 2018

The [2+2] cycloaddition is a versatile strategy for the synthesis of strained cyclobutenes high synthetic value. In this study, two efficient intermolecular cycloadditions between different types chloroalkynes and unactivated alkene are realized with gold catalysis. Of significance that reaction works challenging monosubstituted alkenes, which unprecedented in catalysis scarcely documented other metal-catalyzed/promoted reactions; moreover, exhibits excellent regioselectivities, much better than those reported literature. With 1,2-disubstituted largely stereospecific. cyclobutene products can be prepared nearly gram scale readily undergo further reactions including various cross-coupling using C(sp2)–Cl and/or C(sp2)–SPh bond, turn substantially broaden scope accessible enhance utility bimolecular reaction.

Language: Английский

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Recent Advances in the Development of Chiral Gold Complexes for Catalytic Asymmetric Catalysis

Chemistry - An Asian Journal, Journal Year: 2021, Volume and Issue: 16(5), P. 364 - 377

Published: Jan. 2, 2021

Asymmetric gold catalysis has been rapidly developed in the past ten years. Breakthroughs have made by rational design and meticulous selection of chiral ligands. This review summarizes newly gold-catalyzed enantioselective organic transformations recent progress ligand (since 2016), organized according to different types ligands, including bisphosphine monophosphine phosphite-derived N-heterocyclic carbene ligands for asymmetric gold(I) as well heterocyclic oxazoline gold(III) catalysis.

Language: Английский

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A catalytic asymmetric cross-coupling approach to the synthesis of cyclobutanes

Nature Chemistry, Journal Year: 2021, Volume and Issue: 13(9), P. 880 - 886

Published: July 1, 2021

Language: Английский

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Enantioselective Synthesis of Chiral Cyclobutenes Enabled by Brønsted Acid-Catalyzed Isomerization of BCBs

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(39), P. 21152 - 21158

Published: Sept. 21, 2023

Chiral cyclobutene units are commonly found in natural products and biologically active molecules. Transition-metal-catalysis has been extensively used asymmetric synthesis of such structures, while organocatalytic approaches remain elusive. In this study, bicyclo[1.1.0]butanes involved enantioselective transformation for the first time to offer a highly efficient route toward cyclobutenes with good regio- enantiocontrol. The utilization N-triflyl phosphoramide as chiral Brønsted acid promoter enables isomerization process proceed under mild conditions low catalyst loading well functional group compatibility. resulting could serve platform molecules downstream manipulations excellent reservation stereochemical integrity, demonstrating synthetic practicality developed method. Control experiments have also performed verify formation key carbocation intermediate at benzylic position.

Language: Английский

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Cobalt-Catalyzed Diastereo- and Enantioselective Carbon–Carbon Bond Forming Reactions of Cyclobutenes

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(6), P. 3588 - 3598

Published: Feb. 3, 2023

Catalytic enantioselective functionalization of cyclobutenes constitutes a general and modular strategy for construction enantioenriched complex cyclobutanes bearing multiple stereogenic centers, as chiral four-membered rings are common motifs in biologically active molecules versatile intermediates organic synthesis. However, synthesis through such remained significantly limited. Herein, we report series unprecedented cobalt-catalyzed carbon-carbon bond forming reactions that initiated carbometalation. The protocols feature diastereo- introduction allyl, alkynyl, functionalized alkyl groups. Mechanistic studies indicated an unusual 1,3-cobalt migration subsequent β-carbon elimination cascade process occurred the allyl addition. These new discoveries established elementary cobalt catalysis extension diversity nucleophiles transformations cyclobutenes.

Language: Английский

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Photochemical α-selective radical ring-opening reactions of 1,3-disubstituted acyl bicyclobutanes with alkyl halides: modular access to functionalized cyclobutenes

Chemical Science, Journal Year: 2023, Volume and Issue: 14(45), P. 13060 - 13066

Published: Jan. 1, 2023

Although ring-opening reactions of bicyclobutanes bearing electron-withdrawing groups, typically with β-selectivity, have evolved as a powerful platform for synthesis cyclobutanes, their application in the cyclobutenes remains underdeveloped. Here, novel visible light induced α-selective radical reaction 1,3-disubstituted acyl alkyl precursors functionalized is described. In particular, primary, secondary, and tertiary halides are all suitable substrates this photocatalytic transformation, providing ready access to single all-carbon quaternary center, or two contiguous centers under mild conditions.

Language: Английский

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