‘Almost magical’: chemists can now move single atoms in and out of a molecule’s core

Nature, Journal Year: 2023, Volume and Issue: 618(7963), P. 21 - 24

Published: May 31, 2023

Language: Английский

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Carbon–Carbon Bond Cleavage for Late-Stage Functionalization

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(22), P. 12313 - 12370

Published: Nov. 9, 2023

Late-stage functionalization (LSF) introduces functional group or structural modification at the final stage of synthesis natural products, drugs, and complex compounds. It is anticipated that late-stage would improve drug discovery's effectiveness efficiency hasten creation various chemical libraries. Consequently, products a productive technique to produce product derivatives, which significantly impacts biology development. Carbon-carbon bonds make up fundamental framework organic molecules. Compared with carbon-carbon bond construction, activation can directly enable molecular editing (deletion, insertion, atoms groups atoms) provide more efficient accurate synthetic strategy. However, selective unstrained still one most challenging projects in synthesis. This review encompasses strategies employed recent years for cleavage by explicitly focusing on their applicability functionalization. expands current discourse reactions providing comprehensive overview types bonds. includes C-C(sp), C-C(sp2), C-C(sp3) single bonds; double triple bonds, focus catalysis transition metals organocatalysts. Additionally, specific topics, such as ring-opening processes involving three-, four-, five-, six-membered rings, are discussed, exemplar applications these techniques showcased context bioactive molecules discovery. aims shed light advancements field propose potential avenues future research realm

Language: Английский

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Tunable molecular editing of indoles with fluoroalkyl carbenes

Nature Chemistry, Journal Year: 2024, Volume and Issue: 16(6), P. 988 - 997

Published: March 5, 2024

Language: Английский

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Ring expansion of indene by photoredox-enabled functionalized carbon-atom insertion

Nature Catalysis, Journal Year: 2024, Volume and Issue: 7(3), P. 242 - 251

Published: Jan. 9, 2024

Language: Английский

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Dearomatization of Pyridines: Photochemical Skeletal Enlargement for the Synthesis of 1,2-Diazepines

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(4), P. 2845 - 2854

Published: Jan. 18, 2024

In this report, we developed a unified and standardized one-pot sequence that converts pyridine derivatives into 1,2-diazepines by inserting nitrogen atom. This skeletal transformation capitalizes on the in situ generation of 1-aminopyridinium ylides, which rearrange under UV light irradiation. A thorough evaluation key parameters (wavelength, reaction conditions, activating agent) allowed us to elaborate simple, mild, user-friendly protocol. The model was extrapolated more than 40 examples, including drug derivatives, affording unique 7-membered structures. Mechanistic evidence supports transient presence diazanorcaradiene species. Finally, pertinent transformations products, ring contraction reactions form pyrazoles, were conducted paved way broad application

Language: Английский

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A deconstruction-reconstruction strategy for pyrimidine diversification

Nature, Journal Year: 2024, Volume and Issue: 631(8019), P. 87 - 93

Published: May 2, 2024

Language: Английский

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Spiro-C(sp ³ )-atom transfer: Creating rigid three-dimensional structures with Ph ₂ SCN ₂

Science, Journal Year: 2025, Volume and Issue: 387(6736), P. 885 - 892

Published: Feb. 20, 2025

The introduction of a single C-atom into organic substrates typically results in the formation flat molecules containing unsaturated C(sp)-centers. Adding C(sp3)-atom surrounded by four σ-C-C bonds, which opens up three-dimensional space, is an unresolved problem synthetic chemistry. We report synthesis and application diazosulfur ylide Ph2S=C=N2 reagent that combines reactivity both sulfur ylides diazo compounds to create carbon spiro-centers general fashion sequential or single-step installation C(sp3)-atom. New C-C C-X (where X O N) bonds can be created around C(sp3)-atom, ultimately extended σ-bonds one step without resorting transition metal catalysis. Ph2SCN2 also used access highly strained frameworks (oxa)spiro[2.2]pentanes as well tricyclic spiro-compounds.

Language: Английский

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Generation of Stereocenters via Single-Carbon-Atom Doping Using N-Isocyanides

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

Published: Feb. 28, 2025

Atomic carbon remains a challenging species for organic synthesis despite its potential to form four covalent bonds in single step. Single-carbon-atom doping (SCAD) offers powerful approach enhancing molecular complexity one process without atom loss. However, synthetically viable SCAD reactions capable of generating stereocenters have not been realized. Here, we report an reaction that creates by unlocking the reactivity (N-isocyanoimino)phosphorane as atomic equivalent. This reagent facilitates single-step conversion various acyl chlorides into homologated α-chloro cyclic ketones, proceeding via formation different bonds: C-Cl, C-H, and two C-C at incorporated atom.

Language: Английский

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One-Carbon Insertion and Polarity Inversion Enabled a Pyrrole Strategy to the Total Syntheses of Pyridine-Containing Lycopodium Alkaloids: Complanadine A and Lycodine

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(40), P. 16383 - 16387

Published: Sept. 27, 2021

Complanadine A and lycodine are representative members of the Lycopodium alkaloids with a characteristic pyridine-containing tetracyclic skeleton. has demonstrated promising neurotrophic activity potential for persistent pain management. Herein we report pyrrole strategy enabled by one-carbon insertion polarity inversion concise total syntheses complanadine lycodine. The use as pyridine precursor allowed rapid construction their skeleton via one-pot Staudinger reduction, amine-ketone condensation, Mannich-type cyclization. group was then converted to desired Ciamician–Dennstedt rearrangement process, which also simultaneously introduced chloride at C3 next C–H arylation. Other key steps include direct anti-Markovnikov hydroazidation, Mukaiyama–Michael addition, Paal–Knorr synthesis. Lycodine were prepared in 8 11 steps, respectively, from readily available known compound.

Language: Английский

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Biocatalytic One-Carbon Ring Expansion of Aziridines to Azetidines via a Highly Enantioselective [1,2]-Stevens Rearrangement

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(11), P. 4739 - 4745

Published: March 8, 2022

We report enantioselective one-carbon ring expansion of aziridines to make azetidines as a new-to-nature activity engineered "carbene transferase" enzymes. A laboratory-evolved variant cytochrome P450BM3, P411-AzetS, not only exerts unparalleled stereocontrol (99:1 er) over [1,2]-Stevens rearrangement but also overrides the inherent reactivity aziridinium ylides, cheletropic extrusion olefins, perform rearrangement. By controlling fate highly reactive ylide intermediates, these evolvable biocatalysts promote transformation which cannot currently be performed using other catalyst classes.

Language: Английский

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