An update on chiral phosphoric acid organocatalyzed stereoselective reactions

Organic & Biomolecular Chemistry, Год журнала: 2023, Номер 21(17), С. 3477 - 3502

Опубликована: Янв. 1, 2023

This review article presents an in-depth analysis of the strategies and methodologies for using chiral phosphoric acids as organocatalysts in asymmetric syntheses from recent literature.

Язык: Английский

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Chiral Inorganic Nanomaterials for Photo(electro)catalytic Conversion

ACS Nano, Год журнала: 2023, Номер 17(17), С. 16326 - 16347

Опубликована: Авг. 4, 2023

Chiral inorganic nanomaterials due to their unique asymmetric nanostructures have gradually demonstrated intriguing chirality-dependent performance in photo(electro)catalytic conversion, such as water splitting. However, understanding the correlation between chiral characteristics and process remains challenging. In this perspective, we first highlight chirality source of briefly introduce photo(electro)catalysis systems. Then, delve into an in-depth discussion effects exerted by photo-electrochemistry properties, while emphasizing emerging for conversion. Finally, challenges opportunities conversion are prospected. This perspective provides a comprehensive overview potential which is beneficial further research area.

Язык: Английский

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Design and Catalytic Asymmetric Synthesis of Furan‐Indole Compounds Bearing both Axial and Central Chirality

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(8)

Опубликована: Дек. 29, 2023

Abstract In the chemistry community, catalytic asymmetric synthesis of furan‐based compounds bearing both axial and central chirality has proven to be a significant but challenging issue owing importance difficulty in constructing such frameworks. this work, we have realized first five‐five‐membered via organocatalytic (2+4) annulation achiral furan‐indoles with 2,3‐indolyldimethanols uncommon regioselectivity. By strategy, furan‐indole were synthesized high yields excellent regio‐, diastereo‐, enantioselectivities. Moreover, theoretical calculations conducted provide an in‐depth understanding reaction pathway, activation mode, origin selectivity.

Язык: Английский

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Discovery and Development of the Enantioselective Minisci Reaction

Accounts of Chemical Research, Год журнала: 2023, Номер 56(14), С. 2037 - 2049

Опубликована: Июль 5, 2023

ConspectusThe class of reactions now known as Minisci is broadly defined the addition nucleophilic carbon-based radicals to basic heteroarenes with subsequent rearomatization form a new carbon–carbon bond. Since pioneering work in 1960s and 1970s, these are widely used medicinal chemistry due ubiquity heterocycles druglike molecules. One long-standing challenges has been that regioselectivity mixtures positional isomers commonly obtained on many substrates if there choice between similarly activated sites. At outset described herein, we hypothesized it may be possible tackle this using catalytic strategy whereby bifunctional Brønsted acid catalyst simultaneously activates heteroarene engages attractive non-covalent interactions incoming nucleophile, resulting proximal attack. Using chiral BINOL-derived phosphoric acids, not only were able achieve goal regiocontrol but also discovered could control absolute stereochemistry at stereocenter formed when prochiral α-amino employed. time, discovery was unprecedented context reactions.This Account details protocol further development, expansion, investigations into mechanism have carried out since then, several collaboration other research groups. Collaborative efforts involved an expansion scope diazines guided by multivariate statistical analysis through development predictive model (collaboration Sigman). Also, mechanistic study involving detailed DFT Goodman Ermanis) unveiled selectivity-determining step being deprotonation key cationic radical intermediate associated phosphate anion. We additionally number synthetic developments such removing need prefunctionalize nucleophile; hydrogen-atom transfer can enable formal coupling two C–H bonds C–C bond while retaining high enantio- regioselectivity. Most recently, expand so α-hydroxy used: until point, all examples had concerned radicals. Again, HAT generate radicals, studies (Ermanis) provided insights.Since our original report, appeared exciting from groups applied or different precursors requisite radical. There which alternative photocatalyst systems reduce redox-active esters enantioselective protocol. While primarily Account, contributions will covered briefly for toward end article.

Язык: Английский

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Enantioselective synthesis of molecules with multiple stereogenic elements

Chemical Society Reviews, Год журнала: 2024, Номер 53(22), С. 11165 - 11206

Опубликована: Янв. 1, 2024

This review explores the fascinating world of molecules featuring multiple stereogenic elements, unraveling different strategies designed over years for their enantioselective synthesis.

Язык: Английский

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Cobaltaelectro‐Catalyzed C–H Activation for Central and Axial Double Enantio‐Induction

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(31)

Опубликована: Май 17, 2024

In recent years, enantioselective electrocatalysis has surfaced as an increasingly-effective platform for sustainable molecular synthesis. Despite indisputable progress, strategies that allow the control of two distinct stereogenic elements with high selectivity remain elusive. contrast, we, herein, describe electrochemical cobalt-catalyzed C-H activations enable installation chiral centers along a axis levels enantio- and diastereoselectivities. The developed strategy allowed C-H/N-H activations/annulations cyclic non-cyclic alkenes providing expedient access to various central well atropo-chiral dihydroisoquinolinones paired valuable hydrogen evolution reaction. Studies on atropo-stability obtained compounds demonstrated exceedingly mild conditions ensured by electrocatalytic process were key achieved stereoselectivities.

Язык: Английский

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Recent advances in organocatalytic atroposelective reactions

Beilstein Journal of Organic Chemistry, Год журнала: 2025, Номер 21, С. 55 - 121

Опубликована: Янв. 9, 2025

Axial chirality is present in a variety of naturally occurring compounds, and becoming increasingly relevant also medicine. Many axially chiral compounds are important as catalysts asymmetric catalysis or have chiroptical properties. This review overviews recent progress the synthesis via organocatalysis. Atroposelective organocatalytic reactions discussed according to dominant catalyst activation mode. For covalent organocatalysis, typical enamine iminium modes presented, followed by N -heterocyclic carbene-catalyzed reactions. The bulk devoted non-covalent activation, where Brønsted acids feature most prolific catalytic structure. last part article discusses hydrogen-bond-donating other motifs such phase-transfer catalysts.

Язык: Английский

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Synthesis of Axially Chiral Biaryls via Enantioselective Ullmann Coupling ofortho‐Chlorinated Aryl Aldehydes Enabled by a Chiral 2,2′‐Bipyridine Ligand

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(47)

Опубликована: Окт. 5, 2022

The first nickel-catalyzed highly enantioselective reductive Ullmann coupling of ortho-chlorinated aryl aldehyde was achieved under mild reaction conditions with a chiral 2,2'-bipyridine ligand (+)-DTB-SBpy, thus providing axially biphenyl or binaphthyl dials up to 99 % yield and 99.5:0.5 er. versatility the products as common synthetic intermediates for diverse ligands, catalysts, functional molecules demonstrated by short-step transformations. This protocol also allowed concise formal total synthesis biologically active natural (+)-kotanin, (-)-isoschizandrin (+)-gossypol.

Язык: Английский

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Construction of Acyclic All‐Carbon Quaternary Stereocenters and 1,3‐Nonadjacent Stereoelements via Organo/Metal Dual Catalyzed Asymmetric Allenylic Substitution of Aldehydes

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(20)

Опубликована: Март 13, 2023

A method for the asymmetric construction of functionalized acyclic all-carbon quaternary stereocenters and 1,3-nonadjacent stereoelements has been developed via organo/metal dual catalyzed allenylic substitution branched linear aldehydes, by developing an unknown secondary-secondary diamine as enabling organocatalyst. Although it is believed that diamines are difficult to be used organocatalysts in catalysis, this study demonstrates such can successfully combined with a metal catalyst catalysis. Our enables two important classes motifs which were previously access, axially chiral allene-containing bearing allenyl axial chirality central chirality, good yields high enantio- diastereoselectivity.

Язык: Английский

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Atroposelective Synthesis of Axially Chiral Styrenes by Platinum‐ Catalyzed Stereoselective Hydrosilylation of Internal Alkynes

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(30)

Опубликована: Май 25, 2023

Abstract Hydrofunctionalization of alkynes is one the most efficient ways to access axially chiral styrenes with open‐chained olefins. While great advances have been achieved for 1‐alkynylnaphthalen‐2‐ols and analogues, atroposelective hydrofunctionalization unactivated internal lags. Herein we reported a platinum‐catalyzed hydrosilylation first time. With monodentate TADDOL‐derived phosphonite L1 used as ligand, various were in excellent enantioselectivities high E ‐selectivities. Control experiments showed that N H‐arylamide groups significant effects on both yields could act directing groups. The potential utilities products shown by transformations amide motifs products.

Язык: Английский

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