C−F Bond Activation by Silylium Cation/Phosphine Frustrated Lewis Pairs: Mono‐Hydrodefluorination of PhCF3, PhCF2H and Ph2CF2

Mallov, Ian; Ruddy, Adam J.; Zhu, Hai‐Liang; Grimme, Stefan; Stephan, Douglas W.

doi:10.1002/chem.201705276

Cited by 69 publications

(29 citation statements)

References 75 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In 2017, Grimme and Stephan employed a silylium cation/phosphine frustrated LP to generate a phosphine‐captured arylfluoromethyl cation (Scheme ) . Initially, an intramolecular version was described leading to the CF 2 ‐P linked product 67 .…”

Section: Flp and Lewis Acid Mediated Transformationsmentioning

confidence: 99%

Picking One out of Three: Selective Single C−F Activation in Trifluoromethyl Groups

Jaroschik

2018

Chemistry A European J

150

View full text Add to dashboard Cite

The introduction of a trifluoromethyl (CF ) group into an organic molecule can modify its chemical behavior and lead to changes in its physicochemical and pharmacological properties. The CF group is often chosen for its chemical inertness and stability, which are related to the strong C-F bonds. In recent years, the potential of gaining straightforward access to difluorinated compounds through selective single C-F activation in CF groups has been unveiled. This review describes the latest methodologies for the synthesis of difluoromethylated arenes, difluoroalkenes and difluorinated aldol products of potential synthetic and/or biological interest, employing low-valent metals, transition metal catalysis, FLP and Lewis acid mediated transformations as well as photoredox catalysis.

show abstract

Section: Flp and Lewis Acid Mediated Transformationsmentioning

confidence: 99%

Picking One out of Three: Selective Single C−F Activation in Trifluoromethyl Groups

Jaroschik

2018

Chemistry A European J

150

View full text Add to dashboard Cite

show abstract

“…In ar ecent report, our group developed as toichiometricF LP reagentf or CÀFb ond activation. [28] The salt [C 6 H 4 (1-PPh 2 )(2-SiPh 2 )][B(C 6 F 5 ) 4 ] 15,w hich is an FLP comprised of ap hosphine and as ilylium cation, was shown to react with a,a,a-trifluorotoluene. The product resultsf rom CÀFb ond activation providing the difluorobenzyl-substituted phosphonium centre and a SiÀFb ond in the salt 16.S ubsequent reactionw ith basic hydrolysiso ft his speciesliberated C 6 H 5 CF 2 H, and the corresponding phosphine oxide 17 (Scheme 12).…”

Section: Phosphorus Lewis Bases In Càfactivationmentioning

confidence: 99%

“…In a recent report, our group developed a stoichiometric FLP reagent for C−F bond activation . The salt [C 6 H 4 (1‐PPh 2 )(2‐SiPh 2 )][B(C 6 F 5 ) 4 ] 15 , which is an FLP comprised of a phosphine and a silylium cation, was shown to react with α,α,α‐trifluorotoluene.…”

Section: Phosphorus Lewis Bases In C−f Activationmentioning

confidence: 99%

C−F Bond Activation Mediated by Phosphorus Compounds

Bayne

Stephan

2019

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

The activation and functionalization of CÀFb onds has garnered significant attention in the scientificc ommunity as as trategy to mitigate toxicitya nd environmental concerns, as well as provide new pathways to agro-and pharmaceuticalc hemicals and materials. Although severalt ransition-metal-based systemsh ave been developed for this transformation,t he use of main-group compoundsr emains less explored. In recent years, several strategies for CÀF bond activation have focused on the use of phosphorusbased reagents. In this Minireview,a no verview of strategies is provided that exploits P V andP III -based Lewis acids as well as P III Lewis bases in frustrated Lewis pair (FLP) protocols for hydrodefluorination, CÀCc ouplings andC ÀFd erivatizations.

show abstract

“…[21][22][23][24] Nevertheless, these limitations of boranes drove a substantial amount of research towards exploring new options. 25,26 Recently, group 14 and group 15 LAs were introduced in FLP chemistry including tetrylium [27][28][29][30][31][32][33] and phosphonium LAs. [34][35][36][37][38][39][40][41][42][43][44] Cationic tetrylium LAs were used with amines to effect H2 activation.…”

Section: Introductionmentioning

confidence: 99%

Investigating Tetrel based Neutral Frustrated Lewis Pairs for Hydrogen Activation

Sarkar

Das

Pati

2021

Preprint

View full text Add to dashboard Cite

Tetrel Lewis acids are a prospective alternative to commonly employed neutral boranes in frustrated Lewis pair (FLP) chemistry. While cationic tetrylium Lewis acids, being isolobal and iso(valence)electronic, are a natural replacement to boranes, neutral tetrel Lewis acids allude as less trivial options due to the absence of a formally empty p orbital on the acceptor centre. Recently a series of intramolecular geminal FLPs (C2F5)3E-CH2-P(tBu)2 (E= Si, Ge, Sn) featuring neutral tetrel atoms as acceptor site, were reported for activation of small molecules including H2. In this work, through density functional theory computations, we elucidate the general mechanistic picture of H2 activation by this family of FLPs. Our findings reveal that the acceptor atom derives the required Lewis acidity utilizing the antibonding orbitals of its adjacent bonds with the individual contributions depending on the identity of the acceptor and the donor atoms. By varying the identity of the Lewis acid and Lewis base atoms and attached substituents, we unravel their interplay on the energetics of the H2 activation. We find that switching the donor site from P to N significantly affects the synchronous nature of the bond breaking/formations along the reaction pathway and as a result, N-bearing FLPs have a more favourable H2 activation profile than those with P. Our results are quantitatively discussed in detail within the framework of Activation Strain Model of reactivity along with the Energy Decomposition Analysis method. Finally, the reductive elimination decomposition route pertinent to the plausible extension of the H2 activation to catalytic hydrogenation by these FLPs is also examined

show abstract

C−F Bond Activation by Silylium Cation/Phosphine Frustrated Lewis Pairs: Mono‐Hydrodefluorination of PhCF₃, PhCF₂H and Ph₂CF₂

Cited by 69 publications

References 75 publications

Picking One out of Three: Selective Single C−F Activation in Trifluoromethyl Groups

Picking One out of Three: Selective Single C−F Activation in Trifluoromethyl Groups

C−F Bond Activation Mediated by Phosphorus Compounds

Investigating Tetrel based Neutral Frustrated Lewis Pairs for Hydrogen Activation

Contact Info

Product

Resources

About