Reactions of Fluoroalkenes with an Aluminium(I) Complex

Bakewell, Clare; White, Andrew J. P.; Crimmin, Mark R.

doi:10.1002/anie.201802321

Cited by 105 publications

(66 citation statements)

References 61 publications

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“…Another remarkable achievement from the use of compound 4 was recently reported by Crimmin and co‐workers, they showed it was possible to break strong sp 2 and sp 3 C−F bonds through either oxidative addition at the Al centre or via formation of a metallocyclopropane intermediate which subsequently undergoes α‐ or β‐fluoride elimination.…”

Section: Activation Of Small Molecules With Group 13 Complexesmentioning

confidence: 94%

The Road Travelled: After Main‐Group Elements as Transition Metals

2018

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Since the latter quarter of the twentieth century, main group chemistry has undergone significant advances. Power's timely review in 2010 highlighted the inherent differences between the lighter and heavier main group elements, and that the heavier analogues resemble transition metals as shown by their reactivity towards small molecules. In this concept article, we present an overview of the last 10 years since Power's seminal review, and the progress made for catalytic application. This examines the use of low oxidation state and/or low coordinate group 13 and 14 complexes towards small molecule activation (oxidative addition step in a redox based cycle) and how ligand design plays a crucial role in influencing subsequent reactivity. The challenge in these redox based catalytic cycles still centres on the main group complexes’ ability to undergo reductive elimination, however considerable progress in this field has been reported via reversible oxidative addition reactions. Within the last 5 years the first examples of well‐defined low valent main group catalysts have begun to emerge, representing a bright future ahead for main group chemistry.

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Section: Activation Of Small Molecules With Group 13 Complexesmentioning

confidence: 94%

The Road Travelled: After Main‐Group Elements as Transition Metals

2018

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“…Recently, Crimmin et al. presented oxidative addition reactions of HFO‐1234yf by the activation of the C(sp 2 )−F bond at an aluminium(I) complex …”

Section: Methodsmentioning

confidence: 99%

C−H and C−F Bond Activation Reactions of Fluorinated Propenes at Rhodium: Distinctive Reactivity of the Refrigerant HFO‐1234yf

et al. 2019

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The reaction of [Rh(H)(PEt 3 ) 3 ]( 1)w ith the refrigerant HFO-1234yf (2,3,3,3-tetrafluoropropene) affords an efficient route to obtain [Rh(F)(PEt 3 ) 3 ]( 3)b yC À Fb ond activation. Catalytic hydrodefluorinations were achieved in the presence of the silane HSiPh 3 .Inthe presence of afluorosilane, 3 provides aC ÀHb ond activation followed by a1 ,2-fluorine shift to produce [Rh{(E)-C(CF 3 )=CHF}(PEt 3 ) 3 ]( 4). Similar rearrangements of HFO-1234yf were observed at [Rh(E)-(PEt 3 ) 3 ][E= Bpin (6), C 7 D 7 (8), Me (9)].The ability to favor C À Hb ond activation using 3 and fluorosilane is also demonstrated with 3,3,3-trifluoropropene.S tudies are supported by DFT calculations.

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“…We hypothesised that the defluoroalkylation of HFO-1234yf couldb ea chieved by as tepwise S N 2'/S E 2' reaction sequence mediated by main group reagents. [27,28] The key challenge being the identification of reagentt hat allows control of the selectivity of both steps without loss of fidelity over which site (a or g)o ft he allylic system reacts( Figure 1).…”

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confidence: 99%