Designed Iron Catalysts for Allylic C−H Functionalization of Propylene and Simple Olefins

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(10)

Опубликована: Янв. 9, 2023

Abstract Propylene gas is produced worldwide by steam cracking on million‐metric‐ton scale per year. It serves as a valuable starting material for π‐bond functionalization but rarely applied in transition metal‐catalyzed allylic C−H fine chemical synthesis. Herein, we report that newly‐developed cationic cyclopentadienyliron dicarbonyl complex allows the conversion of propylene to its C−C bond coupling products under catalytic conditions. This approach was also found applicable simple α‐olefins with distinctive branched selectivity. Experimental and computational mechanistic studies supported deprotonation metal‐coordinated alkene turnover‐limiting step led insights into multifaceted roles newly designed ligand promoting enhanced reactivity stereoselectivity.

Язык: Английский

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Direct Access to Quinazolines and Pyrimidines from Unprotected Indoles and Pyrroles through Nitrogen Atom Insertion

Organic Letters, Год журнала: 2023, Номер 25(47), С. 8419 - 8423

Опубликована: Ноя. 20, 2023

Recent advances in single-atom insertion reactions have opened up new synthetic approaches for molecular diversification. Developing innovative strategies to directly transform biologically relevant molecules, without any prefunctionalization, is key further expanding the scope and utility of such transformations. Herein, direct access quinazolines pyrimidines from corresponding unprotected 1H-indoles 1H-pyrroles reported, relying on implementation lithium bis(trimethylsilyl)amide (LiHMDS) as a novel nitrogen atom source combination with commercially available hypervalent iodine reagents. Further application this strategy late-stage settings demonstrates its potential lead structure diversification campaigns.

Язык: Английский

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Reactivity of α-diazo sulfonium salts: rhodium-catalysed ring expansion of indenes to naphthalenes

Chemical Science, Год журнала: 2024, Номер 15(16), С. 5938 - 5943

Опубликована: Янв. 1, 2024

Cyclopropyl-substituted sulfonium salts are obtained by Rh-catalysed addition of α-diazo dibenzothiophenium to olefins. When indenes used as substrates, initially formed cyclopropyl rings open with concomitant elimination dibenzothiophene, enabling access 2-substituted naphthalenes.

Язык: Английский

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Trifluoromethyl Rhodium‐Carbynoid in [2+1+2] Cycloadditions

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(13)

Опубликована: Янв. 18, 2024

Abstract Trifluoromethyl cationic carbyne (CF 3 C + :) possessing dual carbene‐carbocation behavior emulated as trifluoromethyl metal‐carbynoid =M) has not been explored yet, and its reaction characteristics are unknown. Herein, a novel α‐diazotrifluoroethyl sulfonium salt was prepared used in Rh‐catalyzed three‐component [2+1+2] cycloadditions for the first time with commercially available N ‐fused heteroarenes nitriles, yielding series of imidazo[1,5‐ ] ‐heterocycles that interest medicinal chemistry, which insertion Rh‐carbynoid =Rh) into C=N bonds involved. This strategy demonstrates synthetic applications late‐stage modification pharmaceuticals, construction CD ‐containing ‐heterocycles, gram‐scale experiments, synthesis phosphodiesterase 10A inhibitor analog. These highly valuable modifiable exhibit good antitumor activity vitro, thus demonstrating their potential chemistry.

Язык: Английский

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Asymmetric multi-component trifunctionalization reactions with α-Halo Rh-carbenes

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Фев. 7, 2025

Multi-component multi-functionalization reactions involving active intermediates are powerful tools for rapidly generating a wide array of compounds. Metal carbynoids, with their distinct reactivity, hold great promise developing synthetic methodologies. However, application in catalytic transfer has been hindered by the limited availability suitable precursors. In this study, we investigate potential α-halo Rh-carbenes, leveraging concept metal carbynoids reactions. Through chiral phosphoric acid-catalyzed asymmetric trifunctionalization, have developed method synthesizing variety α-cyclic ketal β-amino esters high yields and excellent enantioselectivity. Our extensive experimental computational studies reveal that Rh-carbenes exhibit carbynoid properties, which facilitate transformation into functionalized Fischer-type through decomposition C-halo bond.

Язык: Английский

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Catalytic Synthesis of Cyclopropenium Cations with Rh-Carbynoids

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(37), С. 16737 - 16743

Опубликована: Сен. 8, 2022

Herein, we report the first catalytic one-step synthesis of cyclopropenium cations (CPCs) with readily available alkynes and hypervalent iodine reagents as carbyne sources. Key to process is generation a novel Rh-carbynoid that formally transfers monovalent cationic carbynes (:+C-R) via an oxidative [2+1] cycloaddition. Our able synthesize new type CPC substituted ester group underpins regioselective attack broad range carbon heteroatomic nucleophiles, thus providing platform for valuable cyclopropenes difficult or not possible make by current methodologies.

Язык: Английский

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One‐Carbon Ring Expansion of Indoles and Pyrroles: A Straightforward Access to 3‐Fluorinated Quinolines and Pyridines

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(5)

Опубликована: Дек. 12, 2023

Abstract 3‐Fluorinated quinolines and pyridines are prevalent pharmacophores, yet their synthesis is often challenging. Herein, we demonstrate that dibromofluoromethane as bromofluorocarbene source enables the one‐carbon ring expansion of readily available indoles pyrroles to structurally diverse 3‐fluorinated pyridines. This straightforward protocol requires only a short reaction time ten minutes can be performed under air atmosphere. Preliminary investigations reveal this strategy also applied other valuable azines by using different 1,1‐dibromoalkanes bromocarbene sources.

Язык: Английский

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Organohypervalent heterocycles

Chemical Society Reviews, Год журнала: 2024, Номер 53(9), С. 4786 - 4827

Опубликована: Янв. 1, 2024

This review summarizes structural and synthetic aspects of heterocyclic molecules incorporating an atom a hypervalent main-group element. The higher thermal stability heterocycles, as compared to their acyclic analogs, adds special feature chemistry.

Язык: Английский

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Rh-Catalyzed Enantioselective Single-Carbon Insertion of Alkenes

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(31), С. 21837 - 21846

Опубликована: Июль 26, 2024

The interest in the discovery and development of skeletal editing processes that selectively insert, exchange, or delete an atom organic molecules has significantly increased over last few years. However, this class proceed through creation a chiral center with high asymmetric induction have been largely unexplored. Herein, we report enantioselective single-carbon insertion aryl- alkyl-substituted alkenes mediated by catalytically generated Rh-carbynoid phosphate nucleophiles produce enantioenriched allylic phosphates (enantiomeric ratio (e.r.) = 89.5:10.5-99.5:0.5). key to process was diastereo- cyclopropanation alkene formation transient cyclopropyl-I

Язык: Английский

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Reactions between Diazo Compounds and Hypervalent Iodine(III) Reagents

Angewandte Chemie International Edition, Год журнала: 2020, Номер 59(30), С. 12282 - 12292

Опубликована: Май 19, 2020

Abstract Site‐selective “cut and sew” transformations employing diazo compounds hypervalent iodine(III) involve the departure of leaving groups, a “cut” process, followed by reorganization fragments bond formation, “sew” process. Bearing controllable cleavage sites, play critical role as versatile reagents in wide range organic because their excellent nucleofugality allows for large number unusual reactions to occur. In recent years, combination has emerged promising tool developing new valuable approaches, met considerable success. this Minireview, is systematically illustrated with advances field, aim elaborating synthetic utility potential concept powerful strategy synthesis.

Язык: Английский

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