Accessing Low‐Valent Inorganic Cations by Using an Extremely Bulky N‐Heterocyclic Carbene

Roy, Matthew M. D.; Lummis, Paul A.; Ferguson, Michael J.; McDonald, Robert; Rivard, Eric

doi:10.1002/chem.201703215

Cited by 40 publications

(42 citation statements)

References 48 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…26 The sterically encumbered NHC ligands IMes and IPr, characterized by large percent buried volume parameters (%Vbur) 27,28 of 36.5 and 45.6 (Chart 1a), are widely used in gold catalysis and have enabled some of the best reported activities 5b,29 and selectivities. 6d,h, 30 Gold complexes of NHC and related cyclic alkylaminocarbene (CAAC) ligands with greatly enhanced steric hindrance (%Vbur > 50), such as IPr*, 31 IPr**, 32 ITr, 33 and CAAC-menth 34 (Chart 1b), have been prepared, but investigations of their use in catalysis have so far been limited. 31b,32b,35 Hong and co-worker have provided precedent for highly bulky ADC ligands and their use in gold catalysis (Chart 1c), 16 although these were prepared from amidinium precursors rather than by the isocyanide route.…”

Section: Figure 1 Pertinent Features Of Adc Ligands For Catalysismentioning

confidence: 99%

Highly Sterically Encumbered Gold Acyclic Diaminocarbene Complexes: Overriding Electronic Control in Regiodivergent Gold Catalysis

Ruch¹,

ellison²,

Nguyen³

et al. 2020

Preprint

View full text Add to dashboard Cite

Two series of sterically encumbered gold(I)-acyclic diaminocarbene (ADC) complexes were prepared by reaction of mono- and dialkylamines with gold-bound 2-mesitylphenyl isocyanide (monomesityl series) and 2,6-dimesitylphenyl isocyanide (dimesityl series). X-ray crystal structures and solution 1H NMR data showed that the ADC-gold complexes adopt major rotameric conformations with the bulky biaryl/terphenyl group and one alkyl group located syn to gold. This engenders substantial steric hindrance at the metal, as evidenced by percent buried volume (%Vbur) parameters of 35.7 – 37.2 for the monomesityl series and 46.4 – 52.4 for the dimesityl series. Modest out-of-plane distortions of the ADC N-substituents in the dimesityl series were attributed to attractive CH···π interactions between alkyl groups and mesityl rings on the basis of dispersion-corrected density functional theory calculations. Gold-catalyzed regiodivergent domino cyclization/hydroarylation reactions of a 1,6-enyne with indole revealed that the bulky biaryl/terphenyl substituents of the ligands exert a strong influence on product selectivity, with the bulkier dimesityl ADC-Au catalysts inducing a shift away from the cyclopropane-fused product toward the normally disfavored alkene product. Incorporation of a yet bulkier bis(2,6-diisopropylphenyl)-substituted terphenyl moiety into the ADC led to a gold catalyst that provided exclusive selectivity for the alkene product. Computational modeling suggested that bulky terphenyl groups hinder attack at the a carbon in the initially formed organogold intermediate, allowing steric effects to override the intrinsic electronic preference for the cyclopropane product.

show abstract

Section: Figure 1 Pertinent Features Of Adc Ligands For Catalysismentioning

confidence: 99%

Highly Sterically Encumbered Gold Acyclic Diaminocarbene Complexes: Overriding Electronic Control in Regiodivergent Gold Catalysis

Ruch¹,

ellison²,

Nguyen³

et al. 2020

Preprint

View full text Add to dashboard Cite

show abstract

“…Rivard und seine Gruppe erforschen neue Bindungsarten und phosphoreszierende Materialien auf der Grundlage von Hauptgruppenelementen. Chemistry—A European Journal veröffentlichte einen Beitrag von ihm über die Synthese niedervalenter anorganischer Kationen mithilfe von sperrigen N‐heterocyclischen Carbenen …”

Section: Ausgezeichnet …unclassified

Preise des Chemical Institute of Canada und der Canadian Society for Chemistry

2018

Angewandte Chemie

View full text Add to dashboard Cite

AndrØ B. Charette (UniversitØ de Montreal) nimmt die CIC Medal in Empfang.C harette studierte an der UniversitØ de Montreal und an der University of Rochester,woerunter Anleitung von Robert K. Boeckman, Jr., im Jahr 1987 promovierte.N ach einem Postdoktorat bei David A. Evans an der Harvard University (1987)(1988)(1989) begann er seine unabhängige Laufbahn an der UniversitØ Laval, QuØbec.1994 wechselte er an die UniversitØ de Montreal, an der er zurzeit als Professor fürC hemie tätig ist. Charette und seine Gruppe entwickeln neue Methoden zur stereoselektiven Synthese organischer Verbindungen und Naturstoffe.I nd er Angewandten Chemie berichtete er über die katalytische asymmetrische Synthese hoch funktionalisierter Cyclopropane. [2] Alex Adronov (McMaster University) ist der Gewinner des CIC Macromolecular Science and Engineering Award. Adronov studierte an der McMaster University und promovierte 2001 unter Anleitung von Jean M. J. FrØchet an der University of California, Berkeley.Anschließend kehrte er an die McMaster University zurück, an der er seit 2013 eine Professur innehat. Adronov und seine Gruppe erforschen Design und Synthese von Polymeren mit neuartigen, definierten Strukturen und Eigenschaften. Sein Bericht über das rationale Design konjugierter Polymere zur selektiven Dispergierung metallischer einwandiger Kohlenstoff-Nanorçhren war Titelbildbeitrag in Chemistry-A European Journal.

show abstract

“…Rivard and his group are interested in the discovery of new bonding paradigms and the development of phosphorescent materials based on main‐group elements. He has reported in Chemistry—A European Journal on the use of bulky N‐heterocyclic carbenes to access low‐valent inorganic cations …”

Section: Awarded …mentioning

confidence: 99%

“…[7] Eric Rivard (University of Alberta) is the winner of the CSC Strem Chemicals Award for Pure or Applied Inorganic Chemistry.R ivard studied at the University of New Brunswick, and worked with Ian Manners at the University of Toronto for his H eh as reported in Chemistry-A European Journal on the use of bulky N-heterocyclic carbenes to access lowvalent inorganic cations. [8] William D. Lubell (UniversitØ de MontrØal) has been honored with the CSC Te va Canada Limited Biological and Medicinal Chemistry (BMC) Lectureship Award. Lubell studied at Columbia University,a nd carried out his PhD (completed in 1989) with Henry Rapoport at the University of California, Berkeley.F rom 1990-1991, he was a postdoctoral fellow with RyōjiN oyori at Nagoya University,and in 1991, he joined the faculty at the UniversitØ de MontrØal, where he was made professor in 2004.…”

mentioning

confidence: 99%

Chemical Institute of Canada and Canadian Society for Chemistry Awards

2018

Angew Chem Int Ed

View full text Add to dashboard Cite

TheC hemical Institute of Canada (CIC) and Canadian Society for Chemistry (CSC) have honored several outstanding scientists in their 2018 awards scheme.W ec ongratulate all the winners and feature those were not already highlighted in this section and are connected with Angewandte Chemie and its sister journals as authors,b oard members,o rr eviewers.O ther awardees who were previously featured here include Jillian M. Buriak

show abstract

Accessing Low‐Valent Inorganic Cations by Using an Extremely Bulky N‐Heterocyclic Carbene

Cited by 40 publications

References 48 publications

Highly Sterically Encumbered Gold Acyclic Diaminocarbene Complexes: Overriding Electronic Control in Regiodivergent Gold Catalysis

Highly Sterically Encumbered Gold Acyclic Diaminocarbene Complexes: Overriding Electronic Control in Regiodivergent Gold Catalysis

Preise des Chemical Institute of Canada und der Canadian Society for Chemistry

Chemical Institute of Canada and Canadian Society for Chemistry Awards

Contact Info

Product

Resources

About