C(sp3)–C(sp3) bond formation through nitrogen deletion of secondary amines using O-diphenylphosphinylhydroxylamine

Nature Synthesis, Journal Year: 2024, Volume and Issue: 3(7), P. 913 - 921

Published: June 7, 2024

Language: Английский

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Cascade ring expansion reactions for the synthesis of medium-sized rings and macrocycles

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(38), P. 4999 - 5009

Published: Jan. 1, 2024

This Feature Article discusses recent advances in the development of cascade ring expansion reactions for synthesis medium-sized rings and macrocycles. Cascade have much potential use biologically important macrocycles, most notably as they don't require high dilution conditions, which are commonly used established end-to-end macrocyclisation methods. Operation by method can allow large products to be accessed

Language: Английский

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Expanding the scope of the successive ring expansion strategy for macrocycle and medium-sized ring synthesis: unreactive and reactive lactams

Organic & Biomolecular Chemistry, Journal Year: 2024, Volume and Issue: 22(15), P. 2985 - 2991

Published: Jan. 1, 2024

New Successive Ring Expansion (SuRE) protocols are described for use on unreactive lactams, as well iminosugar derived lactams.

Language: Английский

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Enzymatic ester bond formation strategies in fungal macrolide skeletons

Natural Product Reports, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

This review mainly focuses on the essential roles of thioesterase and condensation domains in fungal macrolide biosynthesis their chemoenzymatic applications. It also discusses differences ester bond formation between fungi bacteria.

Language: Английский

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Stereoselective Synthesis of Atropisomeric Amides Enabled by Intramolecular Acyl Transfer

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A stereoselective strategy to make C–N atropisomeric amides based on intramolecular acyl transfer via a tethered Lewis basic pyridine or tertiary amine group is reported.

Language: Английский

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C–C Cleavage/Cross-Coupling Approach for the Modular Synthesis of Medium-to-Large Sized Rings: Total Synthesis of Resorcylic Acid Lactone Natural Products

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: March 5, 2025

The chemical synthesis of medium (8-11 membered) and large sized (≥12 cyclic systems is often challenging. introduction transannular strain loss degrees freedom in forming macrocycles result poor reaction kinetics thermodynamics (i.e., thermodynamically disfavored at equilibrium). To address these challenges, we herein report a strategy for the medium-to-large rings, which leverages strain-release metal templating through palladium-mediated C-C cleavage/cross-coupling. By means DOSY NMR techniques, identified an undesired competing β-hydrogen elimination pathway, was substrate dependent. Using streamlined requisite precursors, our method enables rapid generation complex rings modular fashion C(sp2)-C(sp3) macrocyclization. transformation enabled short total various resorcylic acid lactone (RAL) natural products unnatural analogues late-stage intermediates. A mechanistic proposal macrocyclization supported by computational studies using density functional theory.

Language: Английский

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Synthesis of All Ring Sizes of Medium-Sized Heterocycles Bridged Biaryls via VQM-Enabled Diversity-Oriented Synthetic Strategy

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 25, 2025

Herein, for the first time, controllable, accurate, and diverse synthesis of all ring sizes medium-sized (8- to 11-membered) indole-derived bridged biaryls has been realized by using ingeniously designed o-alkynylnaphthols that feature cyclic amines with adjustable sizes. The transformation may proceed through a DBN-mediated in-situ generation vinylidene ortho-quinone methides/indole-ring formation/ring expansion cascade sequence, which is characterized acceptable excellent yields good functional group tolerance.

Language: Английский

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Synthesis and Elaboration of Medium-Sized Ring Building Blocks Prepared via Cascade Ring Expansion Reactions

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 1, 2025

A general approach is described for the synthesis and elaboration of medium-sized ring mono- difunctionalized 8- or 9-membered lactone building blocks. The lactones are prepared via cascade expansion reactions elaborated Suzuki-Miyaura cross coupling various N-functionalization reactions. This enables efficient access to diverse, blocks in a synthetically challenging under-represented area pharmaceutical chemical space.

Language: Английский

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Nine-Membered Ketolactams by Oxidative Cyclization Expansion

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: May 27, 2025

Considerable progress has been made over decades in synthetic organic chemistry order to build up molecular complexity, often through the design of advanced catalytic systems. Yet, simply exposing molecules benchmark oxidants catalyst free conditions can sometimes lead surprising and highly valuable products. Thus, a method for accessing rare 9-membered ketolactams is herein described, under mild oxidative conditions. Key 18O 17O label experiments revealed an unexpected oxygen atom migration event ring expansion process. The scope, mechanism, applications, 9 7 membered contraction opportunities are discussed.

Language: Английский

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Catalyst-free synthesis of hydrazino-containing glycine derivatives via a diaziridine in-situ formation/ring-opening cascade

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(16), P. 9104 - 9109

Published: Jan. 1, 2024

A green and efficient method for the synthesis of glycine derivatives from amines, azodicarboxylates, diazoalkanes has been developed. This multicomponent reaction occurred under mild conditions in absence any catalysts or additives.

Language: Английский

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