Intramolecular Fluorocyclizations of Unsaturated Carboxylic Acids with a Stable Hypervalent Fluoroiodane Reagent

Enantioselective, Catalytic Fluorolactonization Reactions with a Nucleophilic Fluoride Source

“…21 Furthermore, as demonstrated with 1d , electrophilic fluorolactonizations of disubstituted styrenes are observed to be poorly diastereoselective. The successful introduction of C–F stereocenters in a highly stereocontrolled manner is thus a significant feature of the new catalytic protocol.…”

Advances in Iodine(III)‐Mediated Halogenations: A Versatile Tool to Explore New Reactivities and Selectivities

“…In late 2015, Stuart and co‐workers reported on the fluorocyclization of unsaturated carboxylic acids 28 (Scheme ) . As reported earlier by Wirth and co‐workers for oxidative lactonizations using PhI(OAc) 2 , the obtained products 29 displayed an unusual chemoselectivity regarding the substituents next to the ring oxygen.…”

“…The linear iodonium ion fragment in 35 represents an excellent leaving group and is thus rapidly replaced by an intramolecular nucleophilic attack of the aryl ring. This sequence results in the generation of a phenonium ion 37 , an intermediate already observed in several hypervalent λ 3 ‐iodane reactions . The cyclopropyl moiety in 37 is then trapped by a nucleophile either intra‐ or intermolecularly.…”

Intermolecular Palladium‐Catalyzed Oxidative Fluorocarbonylation of Unactivated Alkenes: Efficient Access to β‐Fluorocarboxylic Esters

“…[4] Meanwhile,a lthough much efforts have been paid on the fluorination of carbonyl compounds,m ost reactions are restricted to the synthesis of a-fluoro carbonyl compounds. [7] Among them, fluorinated iodines(III) acting as the highly reactive electrophilic fluorinating reagents have been employed for the fluorination of alkenes,s uch as fluorooxygenation, [8] fluoro-amination, [9] and difluorination [10] of alkenes.I nt hese reactions,t he key iodonium complex int.I was formed initially,f ollowed by sequential double S N 2t ype nucleophilic substitution processes to give final functionalized fluorination products (Scheme 1a). [6] Iodine(III) reagents have been extensively applied in organic chemistry,e specially for the difunctionalization of alkenes.…”

“…The reaction yields could be improved to 60 %b yi ncreasing the amount of [F]-1 (5 equiv,entry 2). Further control experiments revealed that of all the parameters of palladium catalyst, BF 3 ·OEt 2 and CO gas were crucial for the successful transformation (entries [7][8][9]. However,f urther optimizing reaction condition failed to improve yields,b ut with substrate 1a exhausted.…”