Copper-mediated aerobic iodination and perfluoroalkylation of boronic acids with (CF 3 ) 2 CFI at room temperature

Liu, Xi-Hai; Leng, Jing; Jia, Su-Jiao; Hao, Jianhong; Zhang, Fanglin; Qin, Hua‐Li; Zhang, Cheng‐Pan

doi:10.1016/j.jfluchem.2016.07.021

Cited by 22 publications

(10 citation statements)

References 71 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Reaction of 1 with copper chloride in benzene produces the solvated Cu-hfip complex disclosed previously and used extensively in arylboronic acid cross-coupling reactions and others. , Looking to avoid the use of the costlier silver fluoride starting material (928 $/mol), we endeavored to synthesize the Cu complex from commercially available copper fluoride dihydrate (43 $/mol) and triphenylphosphine (45$/3 mol). The choice of copper fluorides is limited, since only a few have been reported and/or isolated, with (PPh 3 ) 3 CuF being successfully used as a source of nucleophilic fluoride.…”

Section: Resultsmentioning

confidence: 80%

“…In reports that explore such reactivity, four reagents stand out: the hfip anion and hfip complexes of cadmium, silver, and copper (Scheme ). Evidently, each system has its own drawbacks, which could possibly be remediated with the development of new hfip organometalllic reagents. Herein, we report the synthesis and characterization of new Cu, Ni, and Ag hfip complexes.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Metal Heptafluoroisopropyl (M-hfip) Complexes for Use as hfip Transfer Agents

et al. 2018

View full text Add to dashboard Cite

New coinage-metal heptafluoroisopropyl (L n Mhfip) complexes are synthesized from the metal fluoride and inexpensive hexafluoropropene (M = Ag, Cu; L = PPh 3 , 2,2,6,6tetramethylpiperidine (Htmp)). Reaction of the silver Htmp complex with a Ni dibromide complex led to efficient hfip transfer to afford L 2 NiBr(hfip) (L = 2-ethylpyridine). Treatment of the Nihfip complex with ZnPh 2 gave the corresponding L 2 NiPh(hfip) complexes, which were investigated for reductive elimination of PhCF(CF 3 ) 2 . Although the desired reductive elimination proved unsuccessful, addition of carbon monoxide to L 2 NiPh(hfip) effected an efficient heptafluoroisopropyl carbonylative crosscoupling. Further, while the silver complex does not undergo hfip transfer to organic electrophiles, the copper complex (phen)(PPh 3 )Cu(hfip) (3b) effectively transfers the hfip unit to various substrates. We investigated the scope of 3b with acid chlorides toward the synthesis of perfluoroisopropyl aryl ketones. Additionally, reaction conditions for hfip transfer to pfluorobenzyl bromide and p-fluorobenzaldehyde were identified. As a bonus, 3b was easily generated on a gram scale using commercially available copper hydride by taking advantage of a rapid hydrodefluorination to generate "Cu−F" in situ. Aspects of the observed reactivity are supported by DFT calculations.

show abstract

Section: Resultsmentioning

confidence: 80%

Section: Introductionmentioning

confidence: 99%

Metal Heptafluoroisopropyl (M-hfip) Complexes for Use as hfip Transfer Agents

et al. 2018

View full text Add to dashboard Cite

show abstract

“…Reagent and solvent charges were further evaluated at the reaction end point . Most notably, an increase in the equivalents of 4 resulted in lower in-process levels of 5 , especially after longer hold points.…”

Section: Introductionmentioning

confidence: 99%

A Radical Addition Approach to a Heptafluoroisopropyl Substituted Arene, Combined with a Highly Diastereoselective Annulation Reaction To Synthesize the Tricyclic Core of BMS-986251

Gallagher

Coombs

Guerrero

et al. 2021

Org. Process Res. Dev.

View full text Add to dashboard Cite

We have devised an asymmetric route to the tricyclic core 10 of BMS-986251. The six-step synthesis utilizes readily available starting materials, involves the one-step installation of the perfluoro isopropyl moiety through a radical mechanism, and leverages a novel diastereoselective annulation to build the pyrrolidine ring. Overall, 10 was obtained in 49% yield as a single stereoisomer in 6 steps and 3 isolations using this new route.

show abstract

“…As a result, nucleophilic trifluoroethylation of any electrophiles still has not been reported! On the other hand, generation of 2,2,2-trifluoroethyl radical is known, although 2,2,2-trifluoro-1-iodoethane (CF 3 CH 2 I) is noticeably more difficult to reduce compared to perfluorinated iodides. , A combination of ascorbic acid and a photocatalyst provides an opportunity for the generation of strongly reducing species by the reductive quenching (Scheme , mode B). It was rewarding to find that our conditions worked well for the addition of partially fluorinated iodides 5 to nitrones (Scheme ).…”

mentioning

confidence: 99%

“…Concerning the reaction mechanism, the reduction potential of the catalyst excited state [Ir(ppy) 2 (dtbbpy)PF 6 , Ir(III)*/Ir(IV), −0.96 V vs SCE] is not strong enough to reduce fluoroalkyl iodides with potentials varying from −1.22 to −1.70 V. , Therefore, the mode B involving the reductive quenching of the photocatalyst by ascorbic acid affording an Ir(II) species [Ir(II)/Ir(III), −1.51 V] is more likely (Scheme ). Nitrones are reduced at potentials around −2 V,suggesting that they are notably less prone to reduction than fluorinated alkyl iodides.…”

mentioning

confidence: 99%

Photocatalytic Reductive Fluoroalkylation of Nitrones

et al. 2018

View full text Add to dashboard Cite

A method for the addition of fluorinated groups to nitrones using an iridium photocatalyst and ascorbic acid as a stoichiometric reducing agent is described. The reaction proceeds through the generation of fluorinated radicals by single-electron reduction of fluorinated alkyl iodides with an iridium complex mediated by visible light. Besides perfluorinated reagents, partially fluorinated alkyl iodides can also be effectively used leading to the products, which cannot be obtained by conventional nucleophilic addition reactions. The resulting hydroxylamines can be readily converted to valuable fluorinated amines by reduction with zinc.

show abstract

Copper-mediated aerobic iodination and perfluoroalkylation of boronic acids with (CF 3 ) 2 CFI at room temperature

Cited by 22 publications

References 71 publications

Metal Heptafluoroisopropyl (M-hfip) Complexes for Use as hfip Transfer Agents

Metal Heptafluoroisopropyl (M-hfip) Complexes for Use as hfip Transfer Agents

A Radical Addition Approach to a Heptafluoroisopropyl Substituted Arene, Combined with a Highly Diastereoselective Annulation Reaction To Synthesize the Tricyclic Core of BMS-986251

Photocatalytic Reductive Fluoroalkylation of Nitrones

Contact Info

Product

Resources

About