Transannular C–H functionalization of cycloalkane carboxylic acids

Nature, Год журнала: 2023, Номер 618(7965), С. 519 - 525

Опубликована: Май 31, 2023

Язык: Английский

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Iridium‐Catalyzed Enantioselective C(sp³)−H Borylation of Aminocyclopropanes

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(19)

Опубликована: Фев. 23, 2022

Abstract Transition‐metal‐catalyzed regio‐ and stereo‐controllable C−H functionalization remains a formidable challenge in asymmetric catalysis. Herein, we disclose the first example of iridium‐catalyzed C(sp 3 )−H borylation aminocyclopropanes by using simple imides as weakly coordinating directing groups under mild reaction conditions. The proceeded via six‐membered iridacycle, affording vast range chiral aminocyclopropyl boronates. current method features broad spectrum functional (36 examples) high enantioselectivities (up to 99 %). We also demonstrated synthetic utility preparative scale borylation, C−B bond transformations, conversion group.

Язык: Английский

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Expedited synthesis of α-amino acids by single-step enantioselective α-amination of carboxylic acids

Nature Synthesis, Год журнала: 2023, Номер 2(7), С. 645 - 652

Опубликована: Март 23, 2023

Abstract The conversion of C‒H bonds to C‒N offers a sustainable and economical strategy for the synthesis nitrogen-containing compounds. However, challenges regarding control regio- stereoselectivity currently limit broad applicability intermolecular C( sp 3 )‒H amination reactions. We address these restrictions by directed nitrene-mediated insertion using metal-coordinating functional group. report highly stereocontrolled, iron-catalysed direct α-amination abundant carboxylic acid feedstock molecules. method provides in single step high-value N -Boc-protected α-monosubstituted α,α-disubstituted α-amino acids, which can then be immediately used applications including solution- solid-phase peptide synthesis. This fulfils important aspects sustainability being efficient utilizing non-toxic, Earth-abundant iron as catalytic metal.

Язык: Английский

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Multiporphyrinic architectures: Advances in structural design for photodynamic therapy

Aggregate, Год журнала: 2023, Номер 5(1)

Опубликована: Сен. 13, 2023

Abstract Rationally designed multiporphyrinic architectures for boosting photodynamic therapy (PDT) have attracted significant attentions recently years due to their great potential light‐mediated generation of reactive oxygen species. However, there is still a gap between the structure design and PDT performance biomedical applications. This tutorial review provides historical overview on (i) basic concept deeply understanding porphyrin‐mediated reactions, (ii) developing strategies constructing porphyrinic architectures, like nanorings, boxes, metal‐organic frameworks (MOFs), covalent‐organic (COFs), vesicles, etc., where we classified into following three categories: multiporphyrin arrays, frameworks, others porphyrin assemblies, (iii) various application scenarios clinical cancer antibacterial infection. Also, existing challenges future perspectives innovation applications are mentioned in end section. Moreover, nanomaterials with atomically precise provide an ideal platform investigating relationship structures outputs, personalized “all‐in‐one” theranostic agents, popularization wider fields.

Язык: Английский

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C–H functionalization with alkenes, allenes, and alkynes by half-sandwich rare-earth catalysts

Tetrahedron, Год журнала: 2023, Номер 135, С. 133323 - 133323

Опубликована: Фев. 23, 2023

Язык: Английский

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Palladium-Catalyzed [3 + 2] Annulation of Aromatic Amides with Maleimides through Dual C–H Activation

Organic Letters, Год журнала: 2023, Номер 25(13), С. 2190 - 2195

Опубликована: Март 26, 2023

A palladium-catalyzed [3 + 2] annulation of substituted aromatic amides with maleimides providing tricyclic heterocyclic molecules in good to moderate yields through weak carbonyl chelation is reported. The reaction proceeds via a dual C-H bond activation where the first takes place selectively at benzylic position followed by second meta afford five-membered cyclic ring. An external ligand Ac-Gly-OH has been used succeed this protocol. plausible mechanism proposed for reaction.

Язык: Английский

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Simple Ether‐Directed Enantioselective C(sp³)−H Borylation of Cyclopropanes Enabled by Iridium Catalysis

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(14)

Опубликована: Фев. 10, 2023

Reported here is an efficient and simple ether-directed iridium-catalyzed enantioselective C(sp3 )-H borylation of cyclopropanes. Various functional groups were well-tolerated, affording a vast array chiral cyclopropanes with high enantioselectivities. We also demonstrated that the turnover numbers current reaction could be up to 335.

Язык: Английский

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Ligand‐Enabled Palladium(II)‐Catalyzed Enantioselective β‐C(sp³)−H Arylation of Aliphatic Tertiary Amides**

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(17)

Опубликована: Март 5, 2023

Amide is one of the most widespread functional groups in organic and bioorganic chemistry, it would be valuable to achieve stereoselective C(sp3 )-H functionalization amide molecules. Palladium(II) catalysis has been prevalently used C-H activation chemistry past decades, however, due weakly-coordinating feature simple amides, challenging their direct with enantiocontrol by PdII catalysis. Our group developed sulfoxide-2-hydroxypridine (SOHP) ligands, which exhibited remarkable activity Pd-catalyzed C(sp2 activation. In this work, we demonstrate that chiral SOHP ligands served as an ideal solution enantioselective amides. Herein, report efficient asymmetric /SOHP-catalyzed β-C(sp3 arylation aliphatic tertiary ligand plays a key role deprotonation-metalation step.

Язык: Английский

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Enantioselective remote methylene C−H (hetero)arylation of cycloalkane carboxylic acids

Science, Год журнала: 2024, Номер 384(6697), С. 793 - 798

Опубликована: Май 16, 2024

Stereoselective construction of γ- and δ-stereocenters in carbonyl compounds is a pivotal objective asymmetric synthesis. Here, we report chiral bifunctional oxazoline-pyridone ligands that enable enantioselective palladium-catalyzed remote γ-C−H (hetero)arylations free cycloalkane carboxylic acids, which are essential carbocyclic building blocks organic The reaction establishes γ-tertiary α-quaternary stereocenters simultaneously up to >99% enantiomeric excess, providing access wide range cyclic synthons bioactive molecules. sequential editing two methylene C–H bonds can be achieved by using with opposite configuration construct carbocycles containing three centers. Enantioselective δ-C−H (hetero)arylation also realized establish particularly challenging classical methodologies.

Язык: Английский

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Catalytic Enantioselective Primary C–H Borylation for Acyclic All-Carbon Quaternary Stereocenters

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(2), С. 1635 - 1643

Опубликована: Янв. 5, 2024

Creating a perfect catalyst to operate enzyme-like chiral recognition has been long-sought aim. A challenging example in this context is constructing acyclic all-carbon quaternary stereogenic centers by transition metal-catalyzed enantioselective C–H activation. We now report highly iridium-catalyzed primary borylation of α-all-carbon substituted 2,2-dimethyl amides enabled tailor-made bidentate boryl ligand (CBL). The success the current transformation attributed CBL/iridium catalyst, which confined pocket. This protocol provides diverse array stereocenters with excellent enantiocontrol and distinct structural features. Computational study reveals that steric hindrance CBL could regulate type dominant orbital interaction between substrate, crucial conferring high induction.

Язык: Английский

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