Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)
Published: Sept. 27, 2024
Language: Английский
Science, Journal Year: 2024, Volume and Issue: 383(6689), P. 1350 - 1357
Published: March 21, 2024
Alcohols represent a functional group class with unparalleled abundance and structural diversity. In an era of chemical synthesis that prioritizes reducing time to target maximizing exploration space, harnessing these building blocks for carbon-carbon bond-forming reactions is key goal in organic chemistry. particular, leveraging single activation mode form new C(sp
Language: Английский
Citations
49
Nature, Journal Year: 2024, Volume and Issue: 628(8006), P. 104 - 109
Published: Feb. 13, 2024
Language: Английский
Citations
40
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(15), P. 10274 - 10280
Published: April 3, 2024
The construction of C(sp3)–C(sp3) bonds remains one the most difficult challenges in cross-coupling chemistry. Here, we report a photoredox/nickel dual catalytic approach that enables simultaneous formation two linkages via trimolecular alkenes with alkyl halides and hypervalent iodine-based reagents. reaction harnesses bimolecular homolytic substitution (SH2) mechanism chemoselective halogen-atom transfer (XAT) to orchestrate regioselective addition electrophilic nucleophilic radicals across unactivated without need for directing auxiliary. Utility is highlighted through late-stage (fluoro)alkylation (trideutero)methylation C═C bearing different patterns, offering straightforward access drug-like molecules comprising sp3-hybridized carbon scaffolds.
Language: Английский
Citations
26
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(12), P. 7942 - 7949
Published: March 12, 2024
Here we report the design of a general, redox-switchable organophosphorus alkyl radical trap that enables synthesis broad range C(sp3)–P(V) modalities. This "plug-and-play" approach relies upon in situ activation alcohols and O═P(R2)H motifs, two broadly available inexpensive sources molecular complexity. The mild, photocatalytic deoxygenative strategy described herein allows for direct conversion sugars, nucleosides, complex pharmaceutical architectures to their analogs. includes facile incorporation medicinally relevant phosphonate ester prodrugs.
Language: Английский
Citations
23
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(18), P. 12300 - 12309
Published: April 24, 2024
Metallaphotoredox cross-coupling is a well-established strategy for generating clinically privileged aliphatic scaffolds via single-electron reactivity. Correspondingly, expanding metallaphotoredox to encompass new C(
Language: Английский
Citations
21
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(4), P. 2351 - 2357
Published: Jan. 17, 2024
Cross-coupling catalysts typically react and unite functionally distinct partners via sequential inner-sphere elementary steps: coordination, migratory insertion, reductive elimination, etc. Here, we report a single catalyst that cross-couples styrenes benzyl bromides iterative outer-sphere metal–ligand-carbon interactions. Each partner forms stabilized radical intermediate, yet heterocoupled products predominate. The system is redox-neutral and, thus, avoids exogenous oxidants, resulting in simple scalable conditions. Numerous variations of alkene hydrobenzylation are made possible, including access to the privileged heterodibenzyl (1,2-diarylethane) motif challenging quaternary carbon variants.
Language: Английский
Citations
19
Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown
Published: Feb. 19, 2025
Radical-radical cross-coupling (RCC) offers a promising approach for carbon-carbon bond formation in organic synthesis, particularly creating complex, three-dimensional molecules. However, achieving both cross- and enantioselectivity RCC reactions has remained significant challenge. Here, we report novel metallaphotoredox platform that enables highly enantioselective decarboxylative coupling of carboxylic acid derivatives with aldehydes. Our strategy leverages independent control over radical generation subsequent through fine-tuning common photocatalyst simple chiral bis(oxazoline) nickel catalyst. This redox-neutral protocol requires no exogenous oxidants or reductants demonstrates broad substrate scope functional group compatibility the synthesis enantioenriched α-aryl α-amino ketones. The ketone products can be readily transformed into valuable β-amino alcohols, streamlining access to these important motifs. Furthermore, showcase potential this more challenging C(sp3)-C(sp3) alkyl-alkyl reactions. unified alkyl-acyl represents advance asymmetric catalysis underscores exploit new mechanisms solve long-standing synthetic problems.
Language: Английский
Citations
3
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(23), P. 15693 - 15700
Published: May 31, 2024
The cross-coupling of aryl bromides with alkenes can provide access to diverse combinatorial chemical space. Two-component couplings between these partners are well-known, but three-component aryl-functionalizations unactivated remain underdeveloped. In particular, the aryl-alkylation would allow for rapid construction molecular complexity and expedient exploration a pharmaceutically relevant C(sp3)-rich structural landscape. Herein, we report general approach toward through triple radical sorting mechanism. Over course reaction, high energy radical, primary hindered alkyl simultaneously formed. Through mediation by nickel-based catalyst, three radicals sorted into productive bond-forming pathways efficient alkenes. A wide range electronically sterically differentiated precursors be used complex scaffolds. This method was further applied synthesis highly substituted semisaturated fused heterocycles.
Language: Английский
Citations
16
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(13), P. 9404 - 9412
Published: March 20, 2024
The catalytic and enantioselective construction of quaternary (all-carbon substituents) stereocenters poses a formidable challenge in organic synthesis due to the hindrance caused by steric factors. One conceptually viable potentially versatile approach is coupling C–C bond through an outer-sphere mechanism, accompanied realization enantiocontrol cooperative catalysis; however, examples such processes are yet be identified. Herein, we present method for creating different compounds with photoredox/Fe/chiral primary amine triple catalysis. This facilitates connection unactivated alkyl source tertiary moiety, which also rare. scalable process exhibits mild conditions, does not necessitate use base, possesses good functional-group tolerance. Preliminary investigations into underlying mechanisms have provided valuable insights reaction pathway.
Language: Английский
Citations
14
ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(17), P. 13451 - 13496
Published: Aug. 26, 2024
Alcohols are abundant with versatile structural variety and have ample use as pivotal functional groups in numerous organic processes. Because of their frequent occurrence enumerable natural products, bioactive molecules, medicinal components, alcohol functionalities provide a promising scope research to advance the operational diversity for improving clinical success. Recent years witnessed design modern C–C C–heteroatom bond-forming approaches easily accessible commercially available unactivated aliphatic alcohols native adaptive sp3 handles, hence offering groundbreaking transformative pathways functionalization complex molecular architectures. The judicial application appropriate activating generate alkyl radical from through C–O bond fragmentation employ it potential alkylating agent unfolds unique synthetic strategies, thereby replacing obvious requirement halides. This review elaborately discusses recent trends regarding using C(sp3)-centered various chemical transformations by exploiting different activation modes disrupter under photoredox catalysis. presentation is organized nature scaffolds, kind formation, progress achieved this domain since original discovery providing illustrative examples mechanistic details, focus on difficulties future prospects.
Language: Английский
Citations
10