α-Fluorination of carbonyls with nucleophilic fluorine

Catalytic C(sp3)–F bond formation: recent achievements and pertaining challenges

“…[39][40][41][42] Nucleophilic fluorination involving stoichiometric amounts of safer nucleophilic agents, such as DAST, Deoxofluor, and XtalFluor-E, have also successfully been achieved in an array of non-catalytic reactions, such as the synthesis of high-value allylic fluorides from allylic alcohols (Scheme 1, entries 1-3). [43][44][45][46][47][48][49][50] However, as these reagents can also mediate a range of non-fluorinating reactions, including cyclodehydration of hydroxyamides and amidation of carboxylic acids (Scheme 1, entries 4 and 5), 51,52 finding the optimal conditions to achieve selective fluorination processes with these reagents is often challenging.…”

“…Despite all of the progress made in the last decades, a large portion of the fluorination methods reported in the literature are not catalytic, 17,[47][48][49][50]53,[57][58][59][60]65,68 and could benefit from the use of catalytic technologies. Indeed, catalytic methods provide a number of additional benefits from both a productivity and sustainability standpoint, and may represent a leap forward in the development of more sustainable fluorination routes.…”

Catalytic Asymmetric Fluorination of Copper Carbene Complexes: Preparative Advances and a Mechanistic Rationale

“…[3][4][5] The alternative approacho fu sing an "umpoled" substrate in combination with an ordinary fluoride salt is currently less developed, despite potentialc hemical virtuesa nd practical advantages. [6][7][8] Ar ecent report on the fluorination of highly electrophilic copperc arbenesg enerated in situ provides an interesting foray in this direction (Scheme1). [9,10] Specifically,i tw as shown that a-diazoesters such as 1a,o nt reatment with catalytic amountso f[ Cu (MeCN) 4 ]PF 6 (or [Cu(OTf)] 2 ·PhMe) and L1 as the preferred ligand, react with excess KF in ab iphasic mixture comprised of hexafluoroisopropanol (HFIP) and 1,2-dichloroethane( DCE) at 40 8Ct og ive the corresponding a-fluoroester 2a in good yield.…”

N‐Arylation of Fluoroalkylamine and Trifluoroacetamide through Cu–Catalysis

“…The fluorination of organic compounds can dramatically change their physical and bio/chemical properties that has made fluorination an invaluable tool for drug discovery . For instance, the introduction of fluorine into β‐position of N‐arylamine and arylamide can protect them against oxidation and enhance bioactivity . β‐CF 3 amine and amide group(CF 3 CH 2 NH 2 , CF 3 CONH 2 ) have been probe more valuable than the parent aniline, thus, the synthesis of β‐CF 3 aryl‐amine and amide have driven much attention over the past few years …”