Category Ranking
98%
Total Visits
921
Avg Visit Duration
2 minutes
Citations
20
Article Abstract
In recent years, gold-catalyzed intermolecular alkyne oxidation by an N-oxide oxidant, which presumably involves a gold carbenoid intermediate, has attracted increasing attention because it circumvents the employment of hazardous and potentially explosive diazocarbonyl compounds as starting materials for carbene generation. More importantly, the development of a catalytic enantioselective version of the reaction can help achieve an array of asymmetric synthesis processes modified from various racemic transformations of the gold carbenoid intermediate. In this review, we will present an overview of these recent advances in the asymmetric transformations by utilizing chiral ligands, chiral N,N'-dioxides and chiral substrates, aiming to facilitate progress in this fascinating field of research.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1039/c9ob01096c | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Highly Diastereoselective Synthesis of Oxindole-Bearing Pyrroloindoline via Gold Catalyzed Carbophilic Carbene Transfer Reaction.
Chemistry
April 2025
School of Chemistry & Life resources, Renmin University of China, 59# Zhongguancun St., Beijing, 100872, China.
A new type of gold catalyzed intermolecular dearomative cyclization reaction between diazo oxindole and tryptamine has been developed by utilizing the combination of LAuCl/AgPO (L=hexamethyl phosphane triamine) as the catalyst. This method allows for the facile preparation of a series of C-3-oxindole fused pyrroloindoline products in moderate to good yields with high diastereoselectivities. A plausible reaction mechanism, involving a cascade process of regioselective nucleophilic addition of the carbophilic gold carbenoid intermediate onto tryptamine, followed by an intramolecular cyclization, has been proposed, in which, the high diastereoselectivity is attributed to a preferred transition state.
View Article and Find Full Text PDFAu Acyclic (Amino)(N-Pyridinium)carbenoids: Synthesis via Addition of 2-PySeCl to Au-Bound Isonitriles, Structures, and Cytotoxicity.
Int J Mol Sci
January 2025
Research Institute of Chemistry, Peoples' Friendship University of Russia, 6 Miklukho-Maklaya Street, 117198 Moscow, Russia.
In this study, we report the first example of acyclic (amino)(N-pyridinium)carbenoid gold(III) complexes synthesized via a coupling reaction between 2-pyridylselenyl chloride and Au(I)-bound isonitriles. The reaction involves an initial oxidative addition of the Se-Cl moiety to Au(I), followed by the nucleophilic addition of the pyridine fragment to the isonitrile's C≡N bond, furnishing a metallacycle. Importantly, this is the first example of the pyridine acting as a nucleophile towards metal-bound isonitriles.
View Article and Find Full Text PDFGold(I)-Catalyzed [2 + 2] and [3 + 2] Cycloadditions of 1,1-Difluoroallenes with Aldehydes: Switchable Syntheses of Fluorinated Oxetanes and Furans.
Org Lett
April 2025
Division of Chemistry, Faculty of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan.
1,1-Difluoroallenes underwent regioselective [2 + 2] and [3 + 2] cycloadditions with aldehydes using Au(I) catalysts. An AuCl catalyst enabled an α,β-selective [2 + 2] cycloaddition of 1,1-difluoroallenes, yielding ()-3-alkylidene-2,2-difluorooxetanes. Conversely, an AuCl(IPr)-AgSbF catalyst facilitated an α,γ-selective [3 + 2] cycloaddition, followed by dehydrofluorination to produce aromatized 2-fluorofurans.
View Article and Find Full Text PDFNickelacarborane-Supported Bis--heterocyclic Carbenes.
J Am Chem Soc
July 2023
College of Material, Chemistry and Chemical Engineering, Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, No. 2318, Yuhangtang Road, Hangzhou 311121, Zhejiang China.
Metallacarboranes have attracted significant attention due to their unique properties. Considerable efforts have been made on the reactions around the metal centers or the metal ion itself, while transformations of functional groups of the metallacarboranes have been much less explored. We presented here the formation of imidazolium-functionalized nickelacarboranes (), their subsequent conversion to nickelacarborane-supported -heterocyclic carbenoids (NHCs, ), and the reactivities of toward Au(PPh)Cl and Se powder, which resulted in the formation of bis-gold carbene complexes () and NHC selenium adducts ().
View Article and Find Full Text PDFSynthesis of isoxazoloazaborines gold(I)-catalyzed propargyl aza-Claisen rearrangement/borylative cyclization cascade.
Chem Commun (Camb)
February 2022
School of Life Science and Technology, Tokyo Institute of Technology, 4259 Nagatsuta-cho Midori-ku, Yokohama, 226-8503, Japan.
Isoxazoloazaborines 3 and 5 have been synthesized from 4--propargylaminoisoxazole 1 gold(I)-catalyzed propargyl aza-Claisen rearrangement followed by electrophilic borylative cyclization in 27-86% yields. generation of isoxazole 2 having an amino group and allenyl functionality is essential to give highly substituted isoxazoloazaborines 3 and 5, although the conventional propargyl aza-Claisen rearrangement readily affords the corresponding nitrogen-containing heterocycles, such as pyridines and pyrroles. The resulting isoxazoloazaborine 5a underwent the N-O bond insertion of zinc carbenoid to give oxazine-fused azaborine 6 in 48% yield.
View Article and Find Full Text PDF