Enantioconvergent transformations of secondary alcohols through borrowing hydrogen catalysis

Chemical Society Reviews, Год журнала: 2023, Номер 52(16), С. 5541 - 5562

Опубликована: Янв. 1, 2023

Enantioconvergent transformations of racemic secondary alcohols to enantioenriched chiral amines, N-heterocycles, higher-order and ketones through borrowing hydrogen catalysis is covered in this review.

Язык: Английский

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Highly Enantioselective Catalytic Lactonization at Nonactivated Primary and Secondary γ-C–H Bonds

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(32), С. 18094 - 18103

Опубликована: Авг. 4, 2023

Chiral oxygenated aliphatic moieties are recurrent in biological and pharmaceutically relevant molecules constitute one of the most versatile types functionalities for further elaboration. Herein we report a protocol straightforward general access to chiral γ-lactones via enantioselective oxidation strong nonactivated primary secondary C(sp3)–H bonds readily available carboxylic acids. The key enabling aspect is use robust sterically encumbered manganese catalysts that provide outstanding enantioselectivities (up >99.9%) yields 96%) employing hydrogen peroxide as oxidant. resulting immediate interest preparation inter alia natural products recyclable polymeric materials.

Язык: Английский

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Copper-Catalyzed Enantioconvergent Radical N-Alkylation of Diverse (Hetero)aromatic Amines

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(13), С. 9444 - 9454

Опубликована: Март 21, 2024

The 3d transition metal-catalyzed enantioconvergent radical cross-coupling provides a powerful tool for chiral molecule synthesis. In the classic mechanism, bond formation relies on interaction between nucleophile-sequestered metal complexes and radicals, limiting nucleophile scope to sterically uncongested ones. coupling of congested nucleophiles poses significant challenge due difficulties in transmetalation, restricting reaction generality. Here, we describe probable outer-sphere nucleophilic attack mechanism that circumvents challenging transmetalation associated with nucleophiles. This strategy enables general copper-catalyzed N-alkylation aromatic amines secondary/tertiary alkyl halides exhibits catalyst-controlled stereoselectivity. It accommodates diverse amines, especially bulky secondary primary ones deliver value-added (>110 examples). is expected inspire more nucleophiles, particularly ones, accelerate

Язык: Английский

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Manganese‐Catalyzed Mono‐N‐Methylation of Aliphatic Primary Amines without the Requirement of External High‐Hydrogen Pressure

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(13)

Опубликована: Фев. 1, 2024

Abstract The synthesis of mono‐ N ‐methylated aliphatic primary amines has traditionally been challenging, requiring noble metal catalysts and high‐pressure H 2 for achieving satisfactory yields selectivity. Herein, we developed an approach the selective coupling methanol amines, without hydrogen, using a manganese‐based catalyst. Remarkably, up to 98 % with broad substrate scope were achieved at low catalyst loadings. Notably, due weak base‐catalyzed alcoholysis formamide intermediates, our novel protocol not only obviates addition but also prevents side secondary ‐methylation, supported by control experiments density functional theory calculations.

Язык: Английский

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Access to Saturated Aza‐Heterocycles using the Borrowing Hydrogen Methodology

European Journal of Organic Chemistry, Год журнала: 2024, Номер 27(10)

Опубликована: Фев. 9, 2024

Abstract Borrowing hydrogen (BH) has reached a wide attention from the chemistry community as new opportunity to construct efficiently C−N bond (as well C−C or C−S bond). This straightforward strategy is usually supported by relevant organometallic catalysts, involved in dehydrogenation‐reduction processes. concept highlights specifically application of borrowing preparation saturated aza‐heterocycles (piperidines, pyrrolidines and piperazines) extensively present high‐added value molecules pharmaceutical industry over last 40 years using homogenous catalysis particular. A focus will be given appropriate metals (Ru, Ir more recently earth‐abundant metals) used for this transformation. An extension chiral induction order prepare enantiopure N ‐heterocycles also reported.

Язык: Английский

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Multi-hydroxyl POSS supported iridium complexes as a recyclable catalyst for selective synthesis of N-/C-substituted indoles and the total synthesis of HIV-1 fusion inhibitor

Journal of Catalysis, Год журнала: 2023, Номер 429, С. 115205 - 115205

Опубликована: Ноя. 24, 2023

Язык: Английский

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Biocatalytic Hydrogen-Borrowing Cascade in Organic Synthesis

JACS Au, Год журнала: 2024, Номер 4(3), С. 877 - 892

Опубликована: Март 12, 2024

Biocatalytic hydrogen borrowing represents an environmentally friendly and highly efficient synthetic method. This innovative approach involves converting various substrates into high-value-added products, typically via a one-pot, two/three-step sequence encompassing dehydrogenation (intermediate transformation) hydrogenation processes employing the hydride shuffling between NAD(P)+ NAD(P)H. Represented key transformations in include stereoisomer conversion within alcohols, alcohols amines, of allylic to saturated carbonyl counterparts, α,β-unsaturated aldehydes carboxylic acids, etc. The direct transformation methodology benign characteristics have contributed its advancements fine chemical synthesis or drug developments. Over past decades, strategy biocatalysis has led creation diverse catalytic systems, demonstrating substantial potential for straightforward as well asymmetric transformations. perspective serves detailed exposition recent biocatalytic reactions strategy. It provides insights this future development, shedding light on promising prospects field biocatalysis.

Язык: Английский

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Preparation of a novel cadmium-containing coordination polymer and catalytic application in the synthesis of N-alkylated aminoquinoline derivatives via the borrowing hydrogen approach

Dalton Transactions, Год журнала: 2024, Номер 53(11), С. 5064 - 5072

Опубликована: Янв. 1, 2024

Herein, we report an efficient and straightforward approach for the synthesis of

Язык: Английский

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Enantioconvergent Synthesis of Chiral Fluorenols from Racemic Secondary Alcohols via Pd(II)/Chiral Norbornene Cooperative Catalysis

Chemical Science, Год журнала: 2024, Номер 15(21), С. 7975 - 7981

Опубликована: Янв. 1, 2024

An efficient protocol for the asymmetric synthesis of fluorenols has been developed through an enantioconvergent process enabled by Pd(ii)/chiral norbornene cooperative catalysis. This approach allows facile access to diverse functionalized chiral with constantly excellent enantioselectivities, applying readily available racemic secondary ortho-bromobenzyl alcohols and aryl iodides as starting materials.

Язык: Английский

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Enantioselective Borrowing Hydrogen: A Modern Tool to Construct Enantioenriched Molecules

ChemCatChem, Год журнала: 2024, Номер unknown

Опубликована: Июль 2, 2024

Abstract In the quest for more rapid and eco‐compatible preparation of complex molecules from widely available ones, borrowing hydrogen is one most elegant manners to directly functionalize alcohols. Such catalytic cycles reduce synthetic cost, avoid waste additional steps associated with adjusting redox state functionalization carbon chains. this field, last ten years have seen development general strategies control absolute stereochemistry created molecules. This enantiocontrol can arise three distinct cycle, namely initial dehydrogenation, carbonyl or final back‐transfer. review presents different enantioselective approaches developed according these principles highlights great potential transformations, current limitations future challenges.

Язык: Английский

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