Transition-Metal-Free Formation of C–E Bonds (E = C, N, O, S) and Formation of C–M Bonds (M = Mn, Mo) from <i>N</i>-Heterocyclic Carbene Mediated Fluoroalkene C–F Bond Activation

Leclerc, Matthew C.; Gabidullin, Bulat; Gama, Jason G. Da; Daifuku, Stephanie L.; Iannuzzi, Theresa E.; Neidig, Michael L.; Baker, R. Tom

doi:10.1021/acs.organomet.6b00908

Cited by 12 publications

(5 citation statements)

References 82 publications

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“…In both cases the C=C bond of hexafluoropropene is retained in the organoaluminium compound, with comparable bond lengths of 1.310(6) and 1.325(4) Å in 4 a and 4 b , respectively. The precise origin of this selectivity remains somewhat unclear, although the reactivity of hexafluoropropene with 1 is consistent with many examples of addition of nucleophiles to this substrate …”

Section: Figuresupporting

confidence: 55%

Reactions of Fluoroalkenes with an Aluminium(I) Complex

2018

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As eries of industrially relevant fluoroalkenes react with am onomeric Al I complex. These reactions break strong sp 2 and sp 3 C À Fbonds,and result in the formation of adiverse arrayo fo rganoaluminium compounds.M echanistic studies show that two mechanisms are likely in operation:1 )direct oxidative addition of the CÀFbond to Al I occurs with retention of alkene stereochemistry,a nd 2) stepwise formation and decomposition of am etallocyclopropane intermediate occurs with inversion of alkene stereochemistry.A sp art of this mechanistic analysis,w eh ave isolated the first aluminium metallocyclopropane complex from oxidative addition of an alkene to Al I .R emarkably this reaction is reversible and reductive elimination of the alkene occurs at higher temperature reforming Al I .Furthermore,inselected cases the organoaluminium products are susceptible toward b-fluoride elimination to yield adouble C À Factivation pathway.Scheme 1. Reaction of 1 with the stereoisomers of HFO-1234ze.

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Section: Figuresupporting

confidence: 55%

Reactions of Fluoroalkenes with an Aluminium(I) Complex

2018

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“…In both cases the C = Cb ond of hexafluoropropene is retained in the organoaluminium compound, with comparable bond lengths of 1.310(6) and 1.325(4) in 4a and 4b,r espectively.T he precise origin of this selectivity remains somewhat unclear, although the reactivity of hexafluoropropene with 1 is consistent with many examples of addition of nucleophiles to this substrate. [14,[32][33][34][35][36] Expanding the investigation to fluoroalkenes that do not contain sp 2 C À Fb onds leads to equally facile sp 3 C À Fb ond activation. Ther eaction of 1 with 3,3,3-trifluoropropene yields 5 (Scheme 3).…”

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confidence: 99%

Reactions of Fluoroalkenes with an Aluminium(I) Complex

2018

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A series of industrially relevant fluoroalkenes react with a monomeric Al complex. These reactions break strong sp and sp C-F bonds, and result in the formation of a diverse array of organoaluminium compounds. Mechanistic studies show that two mechanisms are likely in operation: 1) direct oxidative addition of the C-F bond to Al occurs with retention of alkene stereochemistry, and 2) stepwise formation and decomposition of a metallocyclopropane intermediate occurs with inversion of alkene stereochemistry. As part of this mechanistic analysis, we have isolated the first aluminium metallocyclopropane complex from oxidative addition of an alkene to Al . Remarkably this reaction is reversible and reductive elimination of the alkene occurs at higher temperature reforming Al . Furthermore, in selected cases the organoaluminium products are susceptible toward β-fluoride elimination to yield a double C-F activation pathway.

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“…Later, when they react nitrogen‐, oxygen‐ and sulfur‐based nucleophiles with 68 a / b , regio‐ and chemoselective Cβ substituted products 73 a – f were observed with the release of fluoride salts (Scheme 39). [85,86] …”

Section: C−f Bond Activation By N‐heterocyclic Carbene and Their Isoe...mentioning

confidence: 99%

C−F Bond Activation and Functionalizations Enabled by Metal‐free NHCs and Their Metal Complexes

Muthuvel

Gandhi

2022

ChemCatChem

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The activation and functionalization of CÀ F bonds in various fluoroorganics were found to be a daunting task owing to their innate inertness. Harnessing the CÀ F bonds will alleviate the toxicity and environmental issues posed by them, and provide new pathways to access value-added products. Although several strategies have been employed such as metal complexes, Brønsted acids, Lewis acids, and photocatalyst to activate the CÀ F bonds, however, the use of NHC or Metal-NHC is relatively scarce. NHCs based catalytic CÀ F activation stands out owing to its easy accessibility, stability, and facile reactivity. Metal-NHCs were exploited in hydrodefluorination, CÀ C, and CÀ B coupling reactions. Additionally, RÀ M(F)(NHC), an oxidative-addition intermediate that was conveniently isolated allows to decode catalytic CÀ F functionalization pathways. This minireview provides the prominence of NHC and metal-NHC in the area of catalytic CÀ F bond functionalization.

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Transition-Metal-Free Formation of C–E Bonds (E = C, N, O, S) and Formation of C–M Bonds (M = Mn, Mo) from N-Heterocyclic Carbene Mediated Fluoroalkene C–F Bond Activation

Cited by 12 publications

References 82 publications

Reactions of Fluoroalkenes with an Aluminium(I) Complex

Reactions of Fluoroalkenes with an Aluminium(I) Complex

Reactions of Fluoroalkenes with an Aluminium(I) Complex

C−F Bond Activation and Functionalizations Enabled by Metal‐free NHCs and Their Metal Complexes

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