Rh(III)-Catalyzed Intra- and Intermolecular 3,4-Difunctionalization of 1,3-Dienes via Rh(III)-π-Allyl Amidation with 1,4,2-Dioxazolones DOI
Finn Burg, Tomislav Rovis

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(15), P. 9690 - 9697

Published: July 26, 2022

We herein report a modular strategy, which enables Rh(III)-catalyzed diastereoselective 3,4-amino oxygenation and diamination of 1,3-dienes using different O- N-nucleophiles in combination with readily available 3-substituted 1,4,2-dioxazolones (78 examples, 37–91% yield). Previous attempts to functionalize the internal double bond rested on use plain alcoholic solvents as nucleophilic coupling partners thus dramatically limiting scope this transformation. have now identified hexafluoroisopropanol non-nucleophilic solvent that allows diverse nucleophiles greatly expands scope, including an unprecedented amino hydroxylation selectively install valuable, unprotected β-amino alcohols across 1,3-dienes. Moreover, various elaborate prove be compatible providing unique access complex organic molecules. Finally, method is employed series intramolecular reactions deliver valuable nitrogen heterocycles well γ- δ-lactones.

Language: Английский

A Brief Introduction to Chemical Reaction Optimization DOI Creative Commons
Connor J. Taylor, Alexander Pomberger, Kobi Felton

et al.

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(6), P. 3089 - 3126

Published: Feb. 23, 2023

From the start of a synthetic chemist's training, experiments are conducted based on recipes from textbooks and manuscripts that achieve clean reaction outcomes, allowing scientist to develop practical skills some chemical intuition. This procedure is often kept long into researcher's career, as new developed similar protocols, intuition-guided deviations through learning failed experiments. However, when attempting understand systems interest, it has been shown model-based, algorithm-based, miniaturized high-throughput techniques outperform human intuition optimization in much more time- material-efficient manner; this covered detail paper. As many chemists not exposed these undergraduate teaching, leads disproportionate number scientists wish optimize their reactions but unable use methodologies or simply unaware existence. review highlights basics, cutting-edge, modern well its relation process scale-up can thereby serve reference for inspired each techniques, detailing several respective applications.

Language: Английский

Citations

210
Enantioselective Synthesis of Nitrogen–Nitrogen Biaryl Atropisomers via Copper-Catalyzed Friedel–Crafts Alkylation Reaction DOI
Xiaomei Wang, Peng Zhang, Qi Xu

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(37), P. 15005 - 15010

Published: Sept. 8, 2021

Nitrogen–nitrogen bonds containing motifs are ubiquitous in natural products and bioactive compounds. However, the atropisomerism arising from a restricted rotation around an N–N bond is largely overlooked. Here, we describe method to access first enantioselective synthesis of biaryl atropisomers via Cu-bisoxazoline-catalyzed Friedel–Crafts alkylation reaction. A wide range axially chiral bisazaheterocycle compounds were efficiently prepared high yields with excellent enantioselectivities desymmetrization kinetic resolution. Heating experiments showed that have rotational barriers.

Language: Английский

Citations

123
Rational design and atroposelective synthesis of N–N axially chiral compounds DOI Creative Commons
Guang‐Jian Mei, Jonathan J. Wong, Wenrui Zheng

et al.

Chem, Journal Year: 2021, Volume and Issue: 7(10), P. 2743 - 2757

Published: Aug. 18, 2021

Language: Английский

Citations

120
Mechanistic snapshots of rhodium-catalyzed acylnitrene transfer reactions DOI
Hoimin Jung, Jeonguk Kweon, Jong‐Min Suh

et al.

Science, Journal Year: 2023, Volume and Issue: 381(6657), P. 525 - 532

Published: July 20, 2023

Rhodium (Rh) acylnitrene complexes are widely implicated in catalytic C-H amidation reactions but have eluded isolation and structural characterization. To overcome this challenge, we designed a chromophoric octahedral Rh complex with bidentate dioxazolone ligand, which photoinduced metal-to-ligand charge transfer initiates amidation. X-ray photocrystallographic analysis of the Rh-dioxazolone allowed elucidation targeted Rh-acylnitrenoid provided firm evidence that singlet nitrenoid species is primarily responsible for acylamino reactions. We also monitored crystallo reaction nucleophile situ-generated Rh-acylnitrenoid, crystallographically traceable system to capture mechanistic snapshots transfer.

Language: Английский

Citations

45
Enantioselective Rh-Catalyzed Azide-Internal-Alkyne Cycloaddition for the Construction of Axially Chiral 1,2,3-Triazoles DOI
Wenting Guo,

Bo‐Han Zhu,

Yi Chen

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(15), P. 6981 - 6991

Published: April 8, 2022

Significant advances have been achieved for the construction of chiral skeletons containing 1,2,3-triazoles via transition-metal-catalyzed asymmetric azide–alkyne cycloaddition; however, most them limited to terminal alkynes in synthesis central chirality desymmetrization and dynamic/dynamic kinetic resolution. Enantioselective azide-internal-alkyne cycloaddition is extremely limited. Moreover, a challenging five-membered (hetero)biaryl axially molecule still underexplored. Herein, we first report an atroposelective atom-economical 1,4,5-trisubstituted 1,2,3-triazoles, directly acting as core units atropisomers, enantioselective Rh-catalyzed (E-RhAAC) internal azides. The reaction demonstrates excellent functional group tolerance, forging variety C–C under mild conditions with moderate yields (up 99% yield) generally high enantioselectivities ee) along specific regiocontrol. origin regio- enantioselectivity control disclosed by density theory (DFT) calculations, providing new guidance facile compounds.

Language: Английский

Citations

57
Synthesis of N-acyl sulfenamides via copper catalysis and their use as S-sulfenylating reagents of thiols DOI Creative Commons
Ziqian Bai, Shiyang Zhu, Yiyao Hu

et al.

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Oct. 28, 2022

Abstract Sulfur–heteroatom bonds such as S–S and S–N are found in a variety of natural products often play important roles biological processes. Despite their widespread applications, the synthesis sulfenamides, which feature that may be cleaved under mild conditions, remains underdeveloped. Here, we report method for N -acyl sulfenamides via copper-catalyzed nitrene-mediated S -amidation reaction thiols with dioxazolones. This is efficient, convenient, broadly applicable. Moreover, resulting -acetyl highly effective -sulfenylation reagents unsymmetrical disulfides conditions. The protocol enables facile access to sterically demanding difficult synthesize by other means.

Language: Английский

Citations

41
Development of a Nickel-Catalyzed N–N Coupling for the Synthesis of Hydrazides DOI Creative Commons
Jay P. Barbor, Vaishnavi N. Nair, Kimberly R. Sharp

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(28), P. 15071 - 15077

Published: July 6, 2023

A nickel-catalyzed N-N cross-coupling for the synthesis of hydrazides is reported. O-Benzoylated hydroxamates were efficiently coupled with a broad range aryl and aliphatic amines via nickel catalysis to form in an up 81% yield. Experimental evidence implicates intermediacy electrophilic Ni-stabilized acyl nitrenoids formation Ni(I) catalyst silane-mediated reduction. This report constitutes first example intermolecular coupling compatible secondary amines.

Language: Английский

Citations

26
Iron-Catalyzed Asymmetric Imidation of Sulfides via Sterically Biased Nitrene Transfer DOI
Zhenzhong Liu, Hongli Wu,

H Huiqi Zhang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(26), P. 18050 - 18060

Published: June 15, 2024

Transition-metal-catalyzed enantioselective nitrene transfer to sulfides has emerged as one of the most powerful strategies for rapid construction enantioenriched sulfimides. However, achieving stereocontrol over highly active earth-abundant transition-metal nitrenoid intermediates remains a formidable challenge compared with precious metals. Herein, we disclose chiral iron(II)/N,N′-dioxide-catalyzed imidation dialkyl and alkyl aryl using iminoiodinanes precursors. A series sulfimides were obtained in moderate-to-good yields high enantioselectivities (56 examples, up 99% yield, 98:2 e.r.). The utility this methodology was demonstrated by late-stage modification complex molecules synthesis insecticide sulfoxaflor related bioactive compounds. Based on experimental studies theoretical calculations, water-bonded high-spin iron species identified key intermediate. observed stereoselectivity original from steric repulsion between amide unit ligand cave bulky substituent sulfides. Additionally, dioxazolones proved be suitable acylnitrene precursors presence an iron(III)/N,N′-dioxide complex, resulting formation enantioselectivity-reversed (14 81% 97:3

Language: Английский

Citations

11
Decarboxylative stereoretentive C–N coupling by harnessing aminating reagent DOI Creative Commons
Jeonguk Kweon,

Bumsu Park,

Dongwook Kim

et al.

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

Published: May 6, 2024

Abstract In recent decades, strategies involving transition-metal catalyzed carbon-carbon or carbon-heteroatom bond coupling have emerged as potent synthetic tools for constructing intricate molecular architectures. Among these, decarboxylative carbon-nitrogen formation using abundant carboxylic acids their derivatives has garnered notable attention accessing alkyl- arylamines, one of key pharmacophores. While several amination methods been developed, the involvement a common carboradical intermediate currently poses challenges in achieving stereospecific transformation toward chiral alkylamines. Herein, we present base-mediated, stereoretentive amidation by harnessing 1,4,2-dioxazol-5-one reactive and robust amidating reagent under transition-metal-free ambient conditions, encompassing all types primary, secondary tertiary acids, thereby providing access to important pharmacophore, α-chiral amines. This method exhibits high functional group tolerance, convenient scalability, ease applicability 15 N-isotope labeling, thus accentuating its utilities. Experimental computational mechanistic investigations reveal sequence elementary steps: i) nucleophilic addition carboxylate dioxazolone, ii) rearrangement form dicarbonyl N-hydroxy intermediate, iii) conversion hydroxamate, followed Lossen-type rearrangement, finally, iv) reaction situ generated isocyanate with leading C–N manner.

Language: Английский

Citations

10
Total Synthesis of Dixiamycins A and B via a Late-Stage N–N Bond Formation under Visible Light Photoredox Catalysis DOI
Rhituparna Nandi, Ranjit Murmu, S. Sadhukhan

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: 27(6), P. 1531 - 1536

Published: Jan. 30, 2025

Intermolecular oxidative N-N bond formation reactions are quite challenging and largely uncharted. linked dimeric indolosesquiterpene alkaloids represent an underexplored class of natural products, strategies for direct dehydrogenative limited. Here, we have reported that a late-stage visible-light photoredox catalysis facilitates formation, leading to the total syntheses atropo-diastereomers dixiamycins A (1a) B (1b).

Language: Английский

Citations

1