Selective Carbon–Carbon Bond Cleavage of Cyclopropanols

Chemical Reviews, Год журнала: 2020, Номер 121(1), С. 3 - 79

Опубликована: Окт. 21, 2020

The carbon–carbon (C–C) bond cleavage of cyclopropanols is a wide area research with much current activity. This review highlights new developments in this over the past two decades. A summary made three main reactivity modes, namely, homoenolate chemistry, β-keto radical and acid-catalyzed ring-opening, as well all other methods for C–C functionalization cyclopropanols, including base-mediated metal-catalyzed insertions eliminations, oxidative fragmentation using hypervalent iodine reagents, reactions donor–acceptor pericylic reactions. Emphasis placed on synthetic utility related derivatives, which have emerged unique three-carbon synthons.

Язык: Английский

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Recent developments on 1,2-difunctionalization and hydrofunctionalization of unactivated alkenes and alkynes involving C–S bond formation

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(5), С. 1322 - 1345

Опубликована: Янв. 1, 2023

Functionalization of alkenes/alkynes is a highly effective route to achieve molecular complexity. This review summarizes recent progresses on the 1,2-difunctionalization/hydrofunctionalization unactivated with C−S bond formation.

Язык: Английский

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Catalytic asymmetric cationic shifts of aliphatic hydrocarbons

Nature, Год журнала: 2024, Номер 625(7994), С. 287 - 292

Опубликована: Янв. 10, 2024

Abstract Asymmetric catalysis is an advanced area of chemical synthesis, but the handling abundantly available, purely aliphatic hydrocarbons has proven to be challenging. Typically, heteroatoms or aromatic substructures are required in substrates and reagents facilitate efficient interaction with chiral catalyst. Confined acids have recently been introduced as tools for homogenous asymmetric catalysis, specifically enable processing small unbiased 1 . However, reactions which both substrate product not previously catalysed by such super strong confined acids. We describe here imidodiphosphorimidate-catalysed Wagner–Meerwein shift alkenyl cycloalkanes cycloalkenes excellent regio- enantioselectivity. Despite their long history high relevance synthesis biosynthesis, utilizing hydrocarbons, those originally reported Wagner Meerwein, had eluded catalysis.

Язык: Английский

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Enantioselective Synthesis of Planar‐Chiral Sulfur‐Containing Cyclophanes by Chiral Sulfide Catalyzed Electrophilic Sulfenylation of Arenes

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(10)

Опубликована: Янв. 17, 2024

Abstract An efficient catalytic asymmetric electrophilic sulfenylation reaction for the synthesis of planar‐chiral sulfur‐containing cyclophanes has been developed first time. This was achieved by using a new Lewis base catalyst and ortho ‐trifluoromethyl‐substituted sulfenylating reagent. Using substrates with low rotational energy barrier, transformation proceeded through dynamic kinetic resolution, high barrier allowed to undergo resolution process. Meanwhile, this compatible desymmetrization process when symmetric were used. Various readily obtained in moderate excellent yields enantioselectivities (up 97 % yield 95 ee). approach used synthesize pharmaceutically relevant molecules. Density functional theory calculations showed that π‐π interactions between sulfenyl group aromatic ring substrate play crucial role enantioinduction reaction.

Язык: Английский

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Enantioselective Construction of Axially Chiral Amino Sulfide Vinyl Arenes by Chiral Sulfide‐Catalyzed Electrophilic Carbothiolation of Alkynes

Angewandte Chemie International Edition, Год журнала: 2020, Номер 59(12), С. 4959 - 4964

Опубликована: Янв. 22, 2020

The enantioselective construction of axially chiral compounds by electrophilic carbothiolation alkynes is disclosed for the first time. This transformation enabled use a Ts-protected bifunctional sulfide catalyst and Ms-protected ortho-alkynylaryl amines (Ts=tosyl; Ms=mesyl). Both arylthiolating trifluoromethylthiolating reagents are suitable this reaction. obtained products vinyl-aryl amino sulfides can be easily converted into biaryl sulfides, sulfoxides, amines, other valuable difunctionalized compounds.

Язык: Английский

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Small rings in the bigger picture: ring expansion of three- and four-membered rings to access larger all-carbon cyclic systems

Chemical Society Reviews, Год журнала: 2021, Номер 50(13), С. 7513 - 7538

Опубликована: Янв. 1, 2021

Ring-expansion of strained small-size rings to forge larger all-carbon ones, allows a rapid build-up molecular complexity.

Язык: Английский

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Catalytic, Enantioselective Sulfenofunctionalization of Alkenes: Development and Recent Advances

Angewandte Chemie International Edition, Год журнала: 2020, Номер 59(45), С. 19796 - 19819

Опубликована: Май 26, 2020

The last decade has witnessed a burgeoning of new methods for the enantioselective vicinal difunctionalization alkenes initiated by electrophilic sulfenyl group transfer. addition sulfenium ions to results in generation chiral, non-racemic thiiranium ions. These highly reactive intermediates are susceptible attack myriad nucleophiles stereospecific ring-opening event afford anti 1,2-sulfenofunctionalized products. practical application ion transfer been enabled advances field Lewis base catalysis. This Review will chronicle initial discovery and characterization followed determination their configurational stability challenges developing variants. Once framework reactivity established, critical analysis pioneering studies be presented. Finally, comprehensive discussion modern synthetic applications categorized around type nucleophile employed sulfenofunctionalization.

Язык: Английский

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Recent development and applications of semipinacol rearrangement reactions

Chemical Science, Год журнала: 2021, Номер 12(27), С. 9262 - 9274

Опубликована: Янв. 1, 2021

The recent development of semipinacol rearrangement is reviewed, highlighting its application in β-functionalized ketone synthesis, quaternary carbon formation and total synthesis.

Язык: Английский

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Chiral Selenide/Achiral Sulfonic Acid Cocatalyzed Atroposelective Sulfenylation of Biaryl Phenols via a Desymmetrization/Kinetic Resolution Sequence

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(7), С. 2943 - 2952

Опубликована: Фев. 10, 2022

Enantioselective synthesis of axially chiral sulfur-containing biaryl derivatives through the electrophilic sulfenylation phenols has been achieved for first time. This catalytic asymmetric system, which involves sequential desymmetrization and kinetic resolution, is enabled by a combination novel 3,3'-disubstituted BINOL-derived selenide catalyst an achiral sulfonic acid. Control experiments computational studies suggest that multiple noncovalent interactions between cocatalysts substrate, especially network hydrogen bond interactions, play crucial role in determining enantioselectivity reactivity.

Язык: Английский

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Recent advances in thiolation via sulfur electrophiles

Organic Chemistry Frontiers, Год журнала: 2022, Номер 9(23), С. 6684 - 6707

Опубликована: Янв. 1, 2022

This review systematically summarizes the recent developments for constructing sulfur compounds from electrophiles, and mechanism mainly involved thirranium ions, ylides, C–S cross coupling electrophilic substitution.

Язык: Английский

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