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

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(20)

Published: Jan. 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.

Language: Английский

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Generation and Radical–Radical Cross-Coupling of Alkenyloxy Radical

Organic Letters, Journal Year: 2024, Volume and Issue: 26(12), P. 2456 - 2461

Published: March 19, 2024

Alkene-attached oxygen radicals are rarely used, as highly reactive incompatible with the alkene moiety. The direct radical–radical cross-coupling of O is also challenging (limited to N–O bond formation) because lack suitable persistent radical species. This study demonstrated feasibility using Breslow intermediate (BIR) a capture unstable π-conjugated and allow C–O cross-coupling.

Language: Английский

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Generation and Radical-Radical Cross-Coupling of Alkenyloxy Radical: Ester and Ketone Synthesis

Published: Jan. 1, 2024

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Language: Английский

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B(C₆F₅)₃‐Catalyzed N‐Allylation of Hydrazines with Allylic Alcohols

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(5), P. 1176 - 1181

Published: Jan. 11, 2024

Abstract An N‐allylation of monosubstituted acyl hydrazines with allylic alcohols has been developed by using B(C 6 F 5 ) 3 catalysis. This protocol allows for convenient access to various synthetically useful N‐allylated hydrazine products in 48–96% yields broad substrate scope and wide functional group compatibility. The operationally simple reaction proceeds without calling stringent removal air moisture, can be readily scaled up gram scale. Preliminary mechanistic studies support the generation an carbon cation that is involved catalytic cycle, via situ formation diallyl ethers as intermediates.

Language: Английский

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Palladium(ii)-catalyzed 1,3-heteroaryl acyloxylation of propargylic electrophiles

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(15), P. 4077 - 4083

Published: Jan. 1, 2024

Here, we report a regio- and stereo-defined 1,3-heteroaryl acyloxylation of 3-substituted propargylic esters with readily available heteroarenes including indoles, pyrroles, furans thiophenes under palladium catalysis.

Language: Английский

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Boron Lewis acid-catalyzed formal insertion of isocyanides into a C–O bond of benzyl esters

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(17), P. 4381 - 4387

Published: Jan. 1, 2023

A boron Lewis acid catalyzed cascade process consisting of a rare isocyanide insertion with benzyl esters and the Mumm rearrangement to afford valuable imides 100% atom utilization.

Language: Английский

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