Recent advances in metal-catalysed asymmetric sigmatropic rearrangements

Chemical Science, Год журнала: 2022, Номер 13(42), С. 12290 - 12308

Опубликована: Янв. 1, 2022

Catalytic asymmetric sigmatropic rearrangements induced by chiral metal catalysis have been intensively explored. This review summarizes recent significant advances, mainly involving [3,3], [2,3] and [1,3]-rearrangements.

Язык: Английский

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Sulfonate N‐Heterocyclic Carbene–Copper Complexes: Uniquely Effective Catalysts for Enantioselective Synthesis of C−C, C−B, C−H, and C−Si Bonds

Angewandte Chemie International Edition, Год журнала: 2020, Номер 59(48), С. 21304 - 21359

Опубликована: Май 4, 2020

A copper-based complex that contains a sulfonate N-heterocyclic carbene ligand was first reported 15 years ago. Since then, these organometallic entities have proven to be uniquely effective in catalyzing an assortment of enantioselective transformations, including allylic substitutions, conjugate additions, proto-boryl additions alkenes, boryl and silyl hydride-allyl alkenyl boronates, boron-containing allyl moieties N-H ketimines. In this review article, we detail the shortcomings state-of-the-art fueled development air stable class, members which can prepared on multigram scale. For each reaction type, when relevant, prior art at time advance involving NHC-Cu catalysts and/or subsequent key developments are briefly analyzed, relevance efficient total or formal synthesis biologically active molecules is underscored. Mechanistic analysis structural attributes responsible for their ability facilitate transformations with high efficiency as well regio- enantioselectivity detailed. This several formerly undisclosed methodological advances mechanistic analyses, latter constitute revision previously proposals.

Язык: Английский

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Strategies for the Catalytic Enantioselective Synthesis of α-Trifluoromethyl Amines

ACS Catalysis, Год журнала: 2020, Номер 10(21), С. 12507 - 12536

Опубликована: Окт. 12, 2020

The exploitation of the

Язык: Английский

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Copper-Catalyzed Umpolung of N-2,2,2-Trifluoroethylisatin Ketimines for the Enantioselective 1,3-Dipolar Cycloaddition with Benzo[b]thiophene Sulfones

Organic Letters, Год журнала: 2022, Номер 24(25), С. 4603 - 4608

Опубликована: Июнь 15, 2022

A copper-catalyzed umpolung of N-2,2,2-trifluoroethylisatin ketimines for the enantioselective 1,3-dipolar cycloaddition with benzo[b]thiophene sulfones was developed. Using a catalyst system consisting an (S,Sp)-tBu-Phosferrox ligand, Cu(OTf)2, and Cs2CO3, range pentacyclic spirooxindoles containing pyrrolidine benzo[b]sulfolane subunits were obtained in high efficiency excellent regio-, diastereo-, enantioselectivites under mild conditions. The practicality versatility reaction also demonstrated.

Язык: Английский

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Enantio- and Diastereoselective Synthesis of Homoallylic α-Trifluoromethyl Amines by Catalytic Hydroalkylation of Dienes

Organic Letters, Год журнала: 2020, Номер 22(4), С. 1681 - 1685

Опубликована: Фев. 4, 2020

We describe a strategy for the enantio- and diastereoselective synthesis of homoallylic α-trifluoromethyl amines by catalytic hydroalkylation terminal dienes. Trifluoromethyl-substituted isatin-derived azadienolate nucleophiles undergo γ-selective alkylation with Pd–DTBM-SEGPHOS catalyst, which additionally promotes regioselective addition to diene delivers products in up 86% yield, 10:1 dr, 97.5:2.5 er.

Язык: Английский

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Transition-Metal-Catalyzed Asymmetric Couplings of α-Aminoalkyl Fragments to Access Chiral Alkylamines

ACS Catalysis, Год журнала: 2021, Номер 11(11), С. 6560 - 6577

Опубликована: Май 19, 2021

Enantiomerically pure alkylamines are pivotal structural elements in a broad range of pharmaceuticals, agrochemicals, natural products, and chemical building blocks. The development useful methodologies for the preparation these alkyamines is one central long-standing challenges facing synthetic chemistry. In recent years, transition-metal-catalyzed enantioselective coupling reactions α-aminoalkyl species have emerged as appealing C–C bond-forming approaches construction chiral alkylamines. This technique remarkable its substantial advantages functional group compatibility, substrate scope, molecular complexity, practicality, which provides complementarity orthogonality to traditional metal-catalyzed amine synthesis. Review underscores advances asymmetric alkylamine bond forming organized by type key intermediates, including (1) couplings α-aminoalkyl-metal species, (2) radicals, (3) imines with carbon electrophiles, (4) enamines mediated M–H species. addition, practicalities such tools also been highlighted total syntheses selected biologically interesting molecules stereoselective assembly challenging target compounds.

Язык: Английский

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Catalytic and Stereoselective Transformations with Easily Accessible and Purchasable Allyl and Alkenyl Fluorides

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(46)

Опубликована: Авг. 26, 2022

Stereochemically defined organofluorine compounds are vital to drug discovery and many applicable catalytic strategies have been introduced for accessing these entities stereoselectively. One approach entails incorporation of a fluorine atom (C-F bond formation) or an moiety (e.g., CF3 CF2 H), another exploits commercially available with one more atoms. Here, we present the state-of-the-art regarding use alkenyl allylic fluorides in preparation stereochemically fluoro-organic molecules. Allylic may be purchased generated from acid, carboxylate salt, ester, aldehyde hydrate, ketone bearing several atoms next carbonyl group. We underscore untapped potential purchasable compounds, fluorides, as launching points development stereoselective processes that value therapeutic science.

Язык: Английский

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Recent Advances in Catalytic [3,3]-Sigmatropic Rearrangements

Catalysts, Год журнала: 2022, Номер 12(2), С. 227 - 227

Опубликована: Фев. 16, 2022

Carbon–carbon bond formation by [3,3]-sigmatropic rearrangement is a fundamental and powerful method that has been used to build organic molecules for long time. Initially, Claisen Cope rearrangements proceeded at high temperatures with limited scopes. By introducing catalytic systems, highly functionalized substrates have become accessible forming complex structures under mild conditions, asymmetric synthesis can be achieved using chiral systems. This review describes recent breakthroughs in since 2016. Detailed reaction mechanisms are discussed enable an understanding of the reactivity selectivity reactions. Finally, this inspires development new cascade pathways employing as related methodologies functional molecules.

Язык: Английский

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Recent advances in the synthesis of chiral α-tertiary aminesviatransition-metal catalysis

Chemical Communications, Год журнала: 2023, Номер 59(28), С. 4099 - 4114

Опубликована: Янв. 1, 2023

Recent progress in the assembly of chiral α-tertiary amines last decade via transition-metal catalysis is summarized.

Язык: Английский

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The Catalytic Asymmetric Allylic Alkylation of Acyclic Enolates for the Construction of Quaternary and Tetrasubstituted Stereogenic Centres

Chemistry - A European Journal, Год журнала: 2024, Номер 30(20)

Опубликована: Янв. 29, 2024

To facilitate the discovery and development of new pharmaceuticals, demand for novel stereofunctionalised building blocks has never been greater. Whilst molecules bearing quaternary tetrasubstituted stereogenic centres are ideally suited to explore untapped areas chemical space, asymmetric construction ofsterically congested carbon remains a longstanding challenge in organic synthesis. The enantioselective assembly acyclic is even more demanding due need restrict much wider range geometries conformations intermediates involved. In this context, catalytic allylicalkylation (AAA) prochiral nucleophiles, namely enolates, become an indispensable tool access linearα-quaternary andα-tetrasubstituted carbonyl compounds. However, unlike AAA cyclic enolates with fixed enolate geometry, achieve high levels stereocontrol stereoselectivity enolisation must be considered. aim review offer acomprehensivediscussion reactions their analogues generate chiral using metal, non-metal dual catalysis, particular focus given control geometry its impact on stereochemical outcome reaction.

Язык: Английский

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