Asymmetric Electrophilic Fluorocyclization with Carbon Nucleophiles

Abstract

Scheme 1. Metal-free asymmetric halocyclization with a C nucleophile. Tf = trifluoromethanesulfonyl.

Stereoselective Haliranium, Thiiranium and Seleniranium Ion‐Triggered Friedel–Crafts‐Type Alkylations for Polyene Cyclizations

“…In 2013, Gouveneur and co‐workers developed a stereoselective method of fluorocyclization for the construction of helical‐shaped tetracyclic structural motifs, 43 and 44 , possessing a fluorine atom at the quaternary stereocenter. For racemic fluorocyclization, various electrophilic fluorinating agents such as Selectfluor, NFSI ( N ‐fluorobenzosulfonimide) and N ‐fluoro‐2,6‐dichloropyridinium triflate 42 were studied.…”

Enantioselective, Catalytic Fluorolactonization Reactions with a Nucleophilic Fluoride Source

“…2a,3 Fluorofunctionalization of alkenes using F + sources is another powerful approach to the enantioselective synthesis of fluorine-containing chiral compounds that allows for the synthesis of highly functionalized products from simple olefin-containing starting materials. 4,5 In reported efforts directed toward enantioselective fluorolactonization reactions, electrophilic fluorinating reagents have been shown to afford γ-butyrolactone products with exocyclic fluoromethyl substituents in moderate-to-high enantioselectivity (Scheme 1, top). 6 We hypothesized that a hypervalent iodine catalysis of a nucleophilic fluorination pathway (“F − ”) could provide a complementary approach to regioisomeric fluorolactone products containing a C–F stereogenic center (Scheme 1, bottom), in a manner analogous to that observed in recently described enantioselective acetoxylactonization reactions.…”

Catalytic Intramolecular Aminofluorination, Oxyfluorination, and Carbofluorination with a Stable and Versatile Hypervalent Fluoroiodine Reagent

“…[ 6c , m , 7 ] A somewhat less developed but very challenging area involves carbofluorination reactions for the synthesis of fluorine-containing isocyclic compounds. [ 8 ] A limited number of reports have also been published on intermolecular aminofluorination[ 9 ] and carbofluorination[ 10 ] reactions.…”