Conclusive evidence on the mechanism of the rhodium-mediated decyanative borylation

Journal of the American Chemical Society
Miguel A EsteruelasAndrea Vélez

Abstract

The stoichiometric reactions proposed in the mechanism of the rhodium-mediated decyanative borylation have been performed and all relevant intermediates isolated and characterized including their X-ray structures. Complex RhCl{xant(P(i)Pr2)2} (1, xant(P(i)Pr2)2 = 9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene) reacts with bis(pinacolato)diboron (B2pin2), in benzene, to give the rhodium(III) derivative RhHCl(Bpin){xant(P(i)Pr2)2} (4) and PhBpin. The reaction involves the oxidative addition of B2pin2 to 1 to give RhCl(Bpin)2{xant(P(i)Pr2)2}, which eliminates ClBpin generating Rh(Bpin){xant(P(i)Pr2)2} (2). The reaction of the latter with the solvent yields PhBpin and the monohydride RhH{xant(P(i)Pr2)2} (6), which adds the eliminated ClBpin. Complex 4 and its catecholboryl counterpart RhHCl(Bcat){xant(P(i)Pr2)2} (7) have also been obtained by oxidative addition of HBR2 to 1. Complex 2 is the promoter of the decyanative borylation. Thus, benzonitrile and 4-(trifluoromethyl)benzonitrile insert into the Rh-B bond of 2 to form Rh{C(R-C6H4)═NBpin}{xant(P(i)Pr2)2} (R = H (8), p-CF3 (9)), which evolve into the aryl derivatives RhPh{xant(P(i)Pr2)2} (3) and Rh(p-CF3-C6H4){xant(P(i)Pr2)2} (10), as a result of the extrusion of CNBpin. The...Continue Reading

References

Jan 1, 1995·Acta Crystallographica. Section A, Foundations of Crystallography·R H Blessing
Feb 21, 2002·Journal of the American Chemical Society·Christopher Krug, John F Hartwig
Aug 9, 2003·Journal of the American Chemical Society·Felicia L TawMaurice Brookhart
Mar 5, 2004·Journal of the American Chemical Society·Christopher Krug, John F Hartwig
Oct 27, 2005·Journal of the American Chemical Society·Stuart A MacgregorVladimir V Grushin
Feb 21, 2007·Angewandte Chemie·Holger Braunschweig
May 25, 2007·Journal of the American Chemical Society·Tülay A AteşinWilliam D Jones
Dec 25, 2007·Acta Crystallographica. Section A, Foundations of Crystallography·George M Sheldrick
Jul 2, 2009·Chemical Communications : Chem Comm·Li DangTodd B Marder
Dec 24, 2009·Chemical Reviews·Ibraheem A I MkhalidJohn F Hartwig
Feb 22, 2011·Chemical Society Reviews·John F Hartwig
Nov 15, 2011·Chemical Communications : Chem Comm·Andrey Y KhalimonGeorgii I Nikonov
Dec 22, 2011·Journal of the American Chemical Society·Mamoru TobisuNaoto Chatani
Apr 5, 2012·Chemical Communications : Chem Comm·Merle ArrowsmithGabriele Kociok-Köhn
Apr 9, 2013·Inorganic Chemistry·Miguel A EsteruelasAndrea Vélez
Apr 30, 2013·Inorganic Chemistry·Joaquín AlósMarta Valencia
Oct 4, 2013·Inorganic Chemistry·Miguel A EsteruelasAndrea Vélez
Jan 11, 2014·Inorganic Chemistry·Joaquín AlósMarta Valencia
Feb 15, 2014·Journal of the American Chemical Society·Terrance J HadlingtonCameron Jones
Feb 21, 2014·Chemical Society Reviews·A RosJ M Lassaletta
Feb 26, 2015·Journal of the American Chemical Society·R Erik Plata, Daniel A Singleton

❮ Previous
Next ❯

Citations

Dec 5, 2019·Angewandte Chemie·Jie LiWanxiang Zhao
Mar 14, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Maia C MurphyStephen A Westcott
Jul 1, 2020·Chemical Reviews·Minyan Wang, Zhuangzhi Shi
Oct 14, 2020·Chemical Reviews·Yoshiaki Nakao

❮ Previous
Next ❯

Related Concepts

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.