Efficacy of radical reactions of isocyanides with heteroatom radicals in organic synthesis DOI Creative Commons
Akiya Ogawa, Yuki Yamamoto

Beilstein Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 20, P. 2114 - 2128

Published: Aug. 26, 2024

Isocyanide is a promising synthetic reagent not only as one-carbon homologation but also nitrogen source for nitrogen-containing molecules. Because of their isoelectronic structure with carbon monoxide, isocyanides react nucleophiles, electrophiles, radicals, and transition metal reagents, are widely used in organic synthesis. On the other hand, use reactions heteroatom radicals limited. However, reaction tool construction molecules modified variety heteroatoms. In this Perspective, we review addition cyclization discuss prospects radicals.

Language: Английский

Visible-Light-Mediated Deaminative Alkylation of Primary Amines with Silacarboxylic Acids via Isonitrile Formation DOI

Carla Pérez-Sánchez,

Thomas Rigotti, Mariola Tortosa

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: 27(2), P. 583 - 587

Published: Jan. 7, 2025

The functionalization of the C–N bond amines is a straightforward strategy for construction complex scaffolds or late-stage pharmaceuticals. Herein, we describe photoredox-catalyzed deaminative alkylation primary amine-derived isonitriles that provides unnatural amino acid derivatives under mild conditions. use silacarboxylic acids as silyl radical precursors enables generation carbon-centered radicals allow Csp3–Csp3 bonds via Giese-type addition, avoiding undesired hydrodeamination product.

Language: Английский

Citations

1
Photocatalytic Strategy for Decyanative Transformations Enabled by Amine-Ligated Boryl Radical DOI Creative Commons

Yuto Yoshida,

Waka Okada,

Kazutake Takada

et al.

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

Published: Jan. 10, 2025

Decyanation after α-functionalization by exploiting the inherent properties of cyano groups enables strategic assembly a carbon scaffold. Herein, we demonstrate an amine-ligated boryl radical-mediated group transfer (CGT) strategy malononitriles under photocatalytic conditions. This allows for cleavage C(sp3)–CN and formation C(sp3)–D C(sp3) to realize decyanative deuteration cyclization via radical-polar crossover. Computational studies successfully demonstrated reactivity CGT promoters can be accurately assessed.

Language: Английский

Citations

0
NHC-BH3-Mediated Reduction of Sulfonyl Hydrazides into Disulfides and Further Cross-Coupling with Chlorostibine and Bioactivities DOI
Wen‐Jun Zhou,

Liyuan Le,

Youwen Chen

et al.

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

Published: Feb. 17, 2025

This paper presents a novel NHC-BH3-promoted one-step synthesis of disulfides and stibine sulfides using odorless sulfonyl hydrazides. The protocol tolerates various functional groups as well heterocyclic compounds. Mechanistic studies show that NHC-BH3 plays two roles: (1) reducing hydrazides into (2) promoting the cross-coupling chlorostibine with disulfides. synthesized also exhibit satisfactory anticancer activity against 4T1 MDA-MB-231 cancerous cells.

Language: Английский

Citations

0
Direct Deoxygenation of Free Alcohols and Ketones DOI Creative Commons
Haoyu Zhang, Guansheng Ma, Hanbo Chen

et al.

JACS Au, Journal Year: 2025, Volume and Issue: unknown

Published: April 11, 2025

This work presents a feasible method for the elimination of alcohol hydroxyls through direct activation typical alkyl alcohols using neutral boron radicals. transformation necessitates proficient reagent capable swiftly activating hydroxyl group to produce radicals, thereby circumventing numerous alternative side reactions associated with group. To implement this method, we have created an innovative photocatalytic reaction system that oxidizes sodium tetraphenylboron which subsequently enable homolytic conversion groups. deoxygenation technique no additional preactivation and yields favorable outcomes majority substrates. The facilitates methylene reduction aldehydes ketones. Mechanistic studies established likely initiates production alcohols, thereafter undergoing dehydroxylation yield methylene-reduced products.

Language: Английский

Citations

0
Hydro- and deutero-deamination of primary amines using O-diphenylphosphinylhydroxylamine DOI Creative Commons
Panpan Ma, Ting Guo, Hongjian Lu

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Nov. 24, 2024

Abstract While selective defunctionalizations are valuable in organic synthesis, hydrodeamination of primary amines poses challenges. Deuterodeamination, analogous to hydrodeamination, presents even greater difficulties due its frequently slower deuteration rate, interference by hydrogenation and constraints deuterated sources. This study introduces a reliable, robust, scalable hydro- deuterodeamination method capable handling various amines. Defined mild reaction conditions, rapid completion, simplified purification facilitated water-soluble byproducts, the leverages deuterium oxide as source employs commercialized O-diphenylphosphinylhydroxylamine for deamination. Applied diverse range biologically active molecules, it has consistently achieved high yields efficient incorporation. By synergizing with site-selective C–H functionalization aliphatic amines, our reveals synthetic strategies utilizing nitrogen atom traceless directing group, encompassing deaminative alkylation, 1,1-deuteroalkylation, 1,1-dialkylation, 1,1,1-deuterodialkylation, arylation, 1,3-deuteroarylation. Emphasizing this innovation, processes degree-controlled have been developed.

Language: Английский

Citations

3
Csp3–Csp2 Coupling of Isonitriles and (Hetero)arenes through a Photoredox-Catalyzed Double Decyanation Process DOI Creative Commons
María Martín, R. Martín Romero, Chiara Portolani

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(23), P. 17286 - 17292

Published: Nov. 8, 2024

Herein, we demonstrate the ability of isonitriles to be used as alkyl radical precursors in a photoredox-catalyzed transformation involving selective C-N cleavage and Csp

Language: Английский

Citations

2
Iridium-Photocatalyzed Hydrodecyanation of Alkyl Isonitriles with NHC–Borane DOI Open Access
Martin Oestreich, Hendrik F. T. Klare,

Emilio Acuña Bolomey

et al.

Synfacts, Journal Year: 2024, Volume and Issue: 20(07), P. 0705 - 0705

Published: June 14, 2024

Key words defunctionalization - hydrodecyanation iridium photocatalysis isonitriles NHC boranes

Language: Английский

Citations

0
Metal-free C–H borylation of heterocycles by merging photoredox and hydrogen atom transfer catalysis DOI

Changfu Wu,

Shuang Luo,

Xiaozu Liu

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(17), P. 4785 - 4793

Published: Jan. 1, 2024

Reported herein is a method that merges organophotoredox and hydrogen atom transfer catalysis to enable the C–H borylation of heterocycles using O 2 as an environmentally friendly oxidant.

Language: Английский

Citations

0
Efficacy of radical reactions of isocyanides with heteroatom radicals in organic synthesis DOI Creative Commons
Akiya Ogawa, Yuki Yamamoto

Beilstein Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 20, P. 2114 - 2128

Published: Aug. 26, 2024

Isocyanide is a promising synthetic reagent not only as one-carbon homologation but also nitrogen source for nitrogen-containing molecules. Because of their isoelectronic structure with carbon monoxide, isocyanides react nucleophiles, electrophiles, radicals, and transition metal reagents, are widely used in organic synthesis. On the other hand, use reactions heteroatom radicals limited. However, reaction tool construction molecules modified variety heteroatoms. In this Perspective, we review addition cyclization discuss prospects radicals.

Language: Английский

Citations

0