Blue Light Induced Insertion of Carbene into C(CO)—C Bonds of 1,3-Diones DOI Open Access

Dan Ba,

Guolin Cheng

Chinese Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 42(9), P. 2888 - 2888

Published: Jan. 1, 2022

Visible light is an ideal "tool" for the green chemical synthesis.Visible light-induced reactions show such advantages as mild reaction conditions, simple equipments and less by-products.Therefore, it has gradually become important method in organic synthesis.Herein blue induced LiBr-promoted carbene insertion of diazoesters into C(CO)-C bonds 1,3-diones synthesis a wide range all-carbon quaternary center-containing 1,4-dione derivatives reported.The features good substrate universality functional group compatibility, therefore efficient strategy 1,4-diones.Keywords light; Lewis acid; carbene; 1,3-dione; carbon-carbon bond cleavage 酮类化合物是天然产物和合成分子中常见的结构 单元, 也是有机合成化学中最基本的合成原料之一 [1] .样的 1,4-二羰基化合物.随后, 金毅课题组 [4] 发现在银 催化剂存在下, β-烯胺酮类化合物也可实现碳-碳键的 卡宾插入/环化串联反应, 生成多取代的吡咯化合物.此 外, 我们课题组实现了铑催化的 1,3-二酮 键 的多组分插入反应 [5] 以及钌催化的 1,3-二酮与锍氧叶立 德卡宾前体的脱酰基偶联反应 [6] .以上反应均需要过渡 金属催化剂的参与, 因此发展条件温和、无过渡金属参 与的 1,3-二羰基化合物与卡宾前体的反应将具有重要意 义.近年来, 蓝光诱导重氮化合物产生卡宾的反应获得 了深入研究 [7] .目前已经实现了卡宾中间体参与的各类 插入反应, 包括 X-H 插入反应(X＝O, N, S, Si) [8] 和 X-C S) [9] .此外, 蓝光诱导重氮化合物参 与的环丙烷、环丙烯 [10] 以及多取代烯烃的合成已有报

Language: Английский

The Carbene Chemistry of N-Sulfonyl Hydrazones: The Past, Present, and Future DOI
Xiaolong Zhang, Paramasivam Sivaguru,

Yongzhen Pan

et al.

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

Published: Jan. 10, 2025

N-Sulfonyl hydrazones have been extensively used as operationally safe carbene precursors in modern organic synthesis due to their ready availability, facile functionalization, and environmental benignity. Over the past two decades, there has tremendous progress chemistry of N-sulfonyl presence transition metal catalysts, under metal-free conditions, or using photocatalysts photoirradiation conditions. Many transfer reactions are unique cannot be achieved by any alternative methods. The discovery novel development highly enantioselective new skeletal editing represent notable recent achievements hydrazones. This review describes overall made hydrazones, organized based on reaction types, spotlighting current state-of-the-art remaining challenges addressed future. Special emphasis is devoted identifying, describing, comparing scope limitations methodologies, key mechanistic scenarios, potential applications complex molecules.

Language: Английский

Citations

3
Triftosylhydrazone in Single-Atom Skeletal Editing DOI
Zhaohong Liu, Xiaolong Zhang, Paramasivam Sivaguru

et al.

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 16, 2024

ConspectusIn the past decade, single-atom skeletal editing, which involves precise insertion, deletion, or exchange of single atoms in core skeleton a molecule, has emerged as promising synthetic strategy for rapid construction diversification complex molecules without laborious de novo processes. Among them, carbene-initiated editing is particularly appealing due to ready availability and diverse reactivities carbene species. The initial endeavors modify heteroarenes through carbon-atom insertion could date back 1881, when Ciamician Denstedt described conversion pyrroles pyridines by trapping haloform-derived free carbene. Despite its potential value, general applicability this one-carbon seen limited progress poor yields harsh reaction conditions. Significant advances via were achieved only 3 years Levin, Ball, Xu, Song, Glorius, others. hallmark these approaches facile halocyclopropanation followed regioselective ring opening facilitated expulsion halide ion. Consequently, specially designed α-halocarbene precursors, such haloform derivatives, α-halodiazoacetates, chlorodiazirines, α-chlorodiazo oxime esters, can be employed achieve Ciamician–Denstedt-type editing. This not limits types functional groups installed on expansion products but also prevents their widespread adoption, especially late-stage contexts. enduring quest develop environmentally friendly versatile superior group compatibility, application diversifications investigation mechanistic insights into carbon reactions remain fundamental objective.In our over 5 years, we have developed o-trifluoromethylbenzenesulfonylhydrazones (named Triftosylhydrazones) operationally safe easily decomposable diazo surrogates explored various challenging catalytic transfer reactions. Recently, put great efforts expanding scope unlocking triftosylhydrazones precursors Since 2018, realized range acyclic 1,3-dicarbonyls with silver carbenes access 1,4-dicarbonyls, proceeding cyclopropanation/ring-opening process. Inspired results, recently demonstrated series transition-metal-catalyzed highly selective medicinally interesting like pyrroles, indoles, 1,2-diazoles carbenic insertion. We then strained three-membered nitrogen- oxygen-containing heterocycles single-carbon atoms. In Account, present an overview achievements heterocycles, organized based three situ-generated key intermediates, cyclopropane, N-ylide, O-ylide from focus scopes, features, applications. hope that Account will provide valuable contribute development new methodologies both chemistry fields.

Language: Английский

Citations

13
Enantioselective Photochemical Carbene Insertion into C–C and C–H Bonds of 1,3-Diketones by a Guanidine-Amide Organocatalyst DOI
Shiyang Li,

Cefei Zhang,

Guihua Pan

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(7), P. 4656 - 4666

Published: March 22, 2023

A visible-light-induced enantioselective free carbene transfer reaction of α-diazoesters with 1,3-diketones is established by utilizing a chiral bifunctional guanidine-amide organocatalyst. Selective insertion into the C–C or C–H bonds 1,3-diketone could be achieved bearing different steric hindrances. The transformations enable preparation series 1,4-diketones quaternary carbon center 2-substituted-1,3-diketones in good enantioselectivities. On basis control experiments and DFT calculation, stepwise triplet coupling pathway suggested. possible mechanism proposed to explain origin high enantioselectivities via hydrogen-bonds electrostatic interactions catalyst.

Language: Английский

Citations

20
Highlighting the Rich Chemistry of the Allenone Moiety DOI Creative Commons
José M. Alonso, Pedro Almendros

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(9), P. 1332 - 1384

Published: March 14, 2023

Abstract Conjugated and non‐conjugated allenones appear as recurring motifs in organic synthesis, natural products mechanistic investigations showing unique properties applications. The ability of to build cycles has provided a direct access strained systems, medium‐sized rings, arenes, heterocycles complex polycycles. In addition, have served models catalysis. critic compilation herein presented will provide an exhaustive overview the synthetic possibilities may offer, which certainly inspire our community their search more efficient methodologies, preparation biological pharmaceutical targets, improve knowledge theoretical chemistry. Great part this review discuss aspects, catalysis innovation insights chemical transformations implying allenone motif. many examples on total synthesis pharmacologically active compounds be described. We hope that attractive chemistry, catalysis, medicinal chemistry communities. magnified image

Language: Английский

Citations

16
Dioxane promoted photochemical O-alkylation of 1,3-dicarbonyl compounds beyond carbene insertion into C–H and C–C bonds DOI

Xinlong Zhou,

Jingjing Jiang, Min Zhang

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(32), P. 4330 - 4333

Published: Jan. 1, 2024

1,4-Dioxane promoted O -alkylation of various 1,3-dicarbonyl compounds beyond previous carbene insertion into C–H and C–C bonds has been disclosed.

Language: Английский

Citations

5
Who is Who in the Carbene Chemistry of N‐Sulfonyl Hydrazones DOI
Paramasivam Sivaguru,

Yongzhen Pan,

Nan Wang

et al.

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: 42(17), P. 2071 - 2108

Published: May 27, 2024

Comprehensive Summary Over the past few decades, N ‐sulfonyl hydrazones have been recognized as alternative precursors for hazardous diazo compounds in organic synthesis, allowing diverse innovative and original chemical transformations that were otherwise difficult to achieve. This critical review summarizes major advancements carbene chemistry of hydrazones. The contents this are organized based on research conducted by leading scientists who made significant contributions field. individual transfer reactions their mechanisms, well potential applications synthesis natural products complex bioactive molecules, thoroughly discussed.

Language: Английский

Citations

4
Rh-Catalyzed Enantioselective Synthesis of Acyclic Quaternary Carbons via Carbene Insertion DOI
Kun He,

Weikun Zeng,

Yingcheng Wang

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 5273 - 5282

Published: March 13, 2025

Language: Английский

Citations

0
Carbenoid Reactions Promoted by Solids: From Lewis to Brønsted Catalysts DOI Creative Commons
Antonio Leyva‐Pérez, Marta Mon,

Yongkun Zheng

et al.

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: April 23, 2025

ConspectusDiazocarbonyl compounds have become essential tools in organic synthesis, due to their ability situ generate reactive carbenes and be inserted a variety of otherwise stable bonds, such as C-H, C-C, H-O, so on. However, soluble metal salt or complex catalyst is generally required selectively activate couple the carbene, metals employed far are expensive (Rh, Au, Ag, Cu) often unrecoverable. It noteworthy that price ligands can make cheaper (i.e., other ligand-free noble catalysts. In realm modern sustainable chemistry, most these methodologies now unacceptable must adapted, simple strategies for include carbene photoactivation use recoverable solid Unfortunately, despite research field insertion reactions has extended more than 50 years, examples with catalysts still minor, efficient only been reported last two decades.This Account shows journey faced by our group eight years find challenging reactions, employing diazocarbonyl precursors. We will contextualize results those previous The discovery 2017 quasi-linear Pd4 cluster stabilized within metal-organic framework (MOF) was able catalyze Büchner spurred design supported clusters reactions. Pd4-MOF could reused 20 times batch implemented flow process. Following this, catalytic solids, including Au Ag metals, not same MOF but also on oxides zeolites supports, showed good activity were reusable.Our temporarily finishes 2024 when "blank" experiments dealuminated zeolite surprisingly revealed this acid, without any metal, easily activates compound catalyzes thus providing cheap, commercially available, reusable Overall, rapid progress solid-catalyzed activation, formation, achieved during moving from difficult prepare based acid zeolites, pointing confined Brønsted acids study near future.

Language: Английский

Citations

0
Doyle–Kirmse Reaction on Alkynyl Hydrazone Carboxylates: Synthesis of 1,4-Allenyne and 1,5-Enyne Thioaryl Carboxylates DOI

Himani Vaid,

Akashdeep Sharma, Paru Jamwal

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(10), P. 2135 - 2140

Published: March 1, 2024

The first Doyle-Kirmse reaction on alkynyl diazoacetates using allyl/propargyl sulfides is reported. development provides diversified 1,5-enyne and 1,4-allenyne thioaryl carboxylates in good yields under ligand-/additive-free AuCl Rh

Language: Английский

Citations

3
Synthesis of Alkynyl Hydrazones from Unprotected Hydrazine and Their Reactivity as Diazo Precursors DOI
Akashdeep Sharma, Paru Jamwal,

Himani Vaid

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(11), P. 1889 - 1894

Published: March 10, 2023

Alkynyl hydrazones are synthesized conveniently from 2-oxo-3-butynoates and hydrazine by suppressing the susceptible formation of pyrazoles. The resultant transformed into alkynyl diazoacetates under metal-free mild oxidative conditions in excellent yields. Further, cyclopropane propargyl silane carboxylates good yields developing an unprecedented copper-catalyzed carbene transfer reaction.

Language: Английский

Citations

7