Herein, we report a gold-catalyzed Heck reaction facilitated by the ligand-enabled Au(I)/Au(III) redox catalysis. The elementary organometallic steps such as migratory insertion and β-hydride elimination have been realized in the catalytic fashion for the first time in gold chemistry. The present methodology not only overcomes the limitations of previously known transition metal-catalyzed Heck reactions such as the requirement of specialized substrates and formation of a mixture of regioisomeric products as a result of the undesirable chain-walking process but also offers complementary regioselectivity as compared to other transition metal catalysis.
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http://dx.doi.org/10.1021/jacs.3c02544 | DOI Listing |
Angew Chem Int Ed Engl
November 2024
Department of Chemistry, Indian Institute of Science Education and Research Bhopal, Bhopal Bypass Road, Bhauri, Bhopal-, 462 066, India.
We recently reported the gold-catalyzed Heck and chain-walking reactions, which utilize migratory insertion, β-hydride elimination steps in a catalytic fashion. Budzelaar et al. in their correspondence state that these reactions proceed through gold-catalyzed alkene heteroarylation followed by acid-mediated elimination and cyclization sequence.
View Article and Find Full Text PDFOrg Lett
September 2023
School of Materials Science & Engineering, Beijing Institute of Technology, Beijing 100081, China.
A gold-catalyzed Heck reaction of aryl and styryl iodides with styrenes was developed. The hemilabile P,N-ligand-assisted gold-catalyzed C(sp)-C(sp) cross-coupling can synthesize stilbenes and bistyryl complexes, with good functional-group tolerance and mild conditions. The elementary organometallic steps of migratory insertion and β-hydride elimination might be involved in this ligand-enabled Au(I)/Au(III)-catalyzed Heck reaction with styrenes.
View Article and Find Full Text PDFJ Am Chem Soc
April 2023
Department of Chemistry, Indian Institute of Science Education and Research Bhopal, Bhauri, Bhopal 462 066, India.
Herein, we report a gold-catalyzed Heck reaction facilitated by the ligand-enabled Au(I)/Au(III) redox catalysis. The elementary organometallic steps such as migratory insertion and β-hydride elimination have been realized in the catalytic fashion for the first time in gold chemistry. The present methodology not only overcomes the limitations of previously known transition metal-catalyzed Heck reactions such as the requirement of specialized substrates and formation of a mixture of regioisomeric products as a result of the undesirable chain-walking process but also offers complementary regioselectivity as compared to other transition metal catalysis.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
August 2022
State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Tianshui Road 222, Lanzhou, 730000, Gansu, P. R. China.
It is reported herein that by exploiting the commonly shared bicyclic decahydroquinoline motif, a gold-catalyzed enamide-alkyne cycloisomerization reaction is developed to access tricyclic cores in a simple way. These tricyclic cores further serve as an advanced platform for the divergent enantioselective collective total syntheses of five Lycopodium alkaloids, belonging to three different structural types, in a concise and protecting-group-free fashion. The key transformations in the second phase include: 1) a transannular reductive Heck cyclization for installation of the azepane ring in fawcettidine, fawcettimine, and lycoposerramine Q; 2) a domino Mukaiyama hydration/Grob fragmentation process for construction of the ten-membered lactam system in phlegmariurine B; 3) a Fukuyama one-pot protocol for the construction of the 2-pyridone motif in lycoposerramine R.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
July 2020
Department of Chemistry, Indian Institute of Science Education and Research Bhopal, Bhauri, Bhopal, 462 066, India.
Herein, we disclose the gold-catalyzed 1,2-diarylation of alkenes through the interplay of ligand-enabled Au /Au catalysis with the idiosyncratic π-activation mode of gold complexes. Unlike the classical migratory-insertion-based approach to 1,2-diarylation, the present approach not only circumvents the formation of direct Ar-Ar' coupling and Heck-type side products but more intriguingly demonstrates reactivity and selectivity complementary to those of previously known metal catalysis (Pd, Ni, or Cu). Detailed investigations to underpin the mechanistic scenario revealed oxidative addition of aryl iodides to an Au complex to be the rate-limiting step owing to the non-innocent nature of the aryl alkene.
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