Hydride abstraction from the neutral gold cycloheptatrienyl complex [(P)Au(η(1)-C7H7)] (P=P(tBu)2(o-biphenyl)) with triphenylcarbenium tetrafluoroborate at -80 °C led to the isolation of the cationic gold cycloheptatrienylidene complex [(P)Au(η(1)-C7H6)](+) BF4(-) in 52% yield, which was characterized in solution and by single-crystal X-ray diffraction. This cycloheptatrienylidene complex represents the first example of a gold carbenoid complex that lacks conjugated heteroatom stabilization of the electron-deficient C1 carbon atom. The cycloheptatrienylidene ligand of this complex is reactive; it can be reduced by mild hydride donors, and converted to tropone in the presence of pyridine N-oxide.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1002/anie.201404882 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Nickelacarborane-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 PDFGold catalyzed efficient preparation of dihydrobenzofuran from 1,3-enyne and phenol.
Chem Commun (Camb)
November 2021
Department of Chemistry, Renmin University of China, 59# Zhongguancun Street, Haidian, Beijing 100872, China.
A gold catalyzed formal intermolecular [2+3] cyclo-coupling of 1,3-enynes with phenols was developed to prepare dihydrobenzofuran derivatives with the addition of 2,6-dichloropyridine -oxide, in which, a highly -selective phenol SAr functionalization was achieved by using 1,3-enynes as α-oxo vinyl gold carbenoid surrogates.
View Article and Find Full Text PDFGold-Catalyzed Annulations with Nucleophilic Nitrenoids Enabled by Heteroatom-Substituted Alkynes.
Chem Rec
December 2021
School of Chemistry, University of Birmingham Edgbaston, Birmingham, B15 2TT, UK.
The combination of a nucleophilic nitrene equivalent, a triple bond and a π-acid catalyst has underpinned numerous efficient transformations for the preparation of azacycles. This personal account details our efforts in developing an annulation strategy. Adding a nucleophilic nitrenoid to an activated alkyne can generate carbenoid character that is then quenched by a cyclisation onto the nitrenoid substituent.
View Article and Find Full Text PDFSynthesis of Pyrrolo[1,2-]isoquinolines via Gold(I)-Catalyzed Cyclization/Enyne Cycloisomerization/1,2-Migration Cascade.
Org Lett
August 2020
Laboratory for Organic & Microwave-Assisted Chemistry (LOMAC), Department of Chemistry, KU Leuven, Celestijnenlaan 200F, B-3001, Leuven, Belgium.
A gold(I)-catalyzed cascade transformation of -alkynic 2-ynamides for the rapid and efficient synthesis of the indolizidine scaffold is developed. Through a sequential nucleophilic cyclization/enyne cycloisomerization/1,2-migration process, diverse pyrrolo[1,2-]isoquinolines are obtained under mild conditions in a regiospecific and convergent manner. Various alkyl and aryl migrating groups are tolerated in this process.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!