2020
DOI: 10.1021/jacs.9b12167
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Frustrated Lewis-Pair-Meditated Selective Single Fluoride Substitution in Trifluoromethyl Groups

Abstract: Single fluoride substitution in trifluoromethylarenes is an ongoing synthetic challenge that often leads to "overreaction", where multiple fluorides are replaced. Development of this reaction would allow simple access to a vast range of difluoromethyl derivatives of current interest to pharmaceutical, agrochemistry, and materials sciences. Using a catalytic frustrated Lewis pair approach, we have developed a generic protocol that allows a single substitution of one fluoride in trifluoromethyl groups with neutr… Show more

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Cited by 137 publications
(110 citation statements)
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“…Conversion to ArCF2X (2a-k) was quantified by 19 F NMR, relative to 4-fluorotoluene (-119.5 ppm). † 3 , 2e 4 , 2f 5 all matched their respective reported 19 F NMR chemical shifts. GC-MS analysis was also performed to verify the identity of these products, using the following method.…”
Section: Bromide Halex Investigation IIsupporting
confidence: 65%
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“…Conversion to ArCF2X (2a-k) was quantified by 19 F NMR, relative to 4-fluorotoluene (-119.5 ppm). † 3 , 2e 4 , 2f 5 all matched their respective reported 19 F NMR chemical shifts. GC-MS analysis was also performed to verify the identity of these products, using the following method.…”
Section: Bromide Halex Investigation IIsupporting
confidence: 65%
“…[2] A prominent example, the trifluoromethyl group (CF3) is present in 24% of drugs globally approved in 2019. [3] The selective conversion of C-F bonds to C-H or C-C bonds in polyfluorinated molecules has enjoyed increased focus as a strategy to access challenging fluorination patterns. [4] A related transformation is the conversion to higher halide C-X bonds (X = Cl, Br, I), through halogen-exchange (halex) reactions.…”
mentioning
confidence: 99%
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“…Activation of the allylic C-F bond could be accomplished through treatment with a Lewis acid (Scheme 35), which was demonstrated by Ichikawa's group [97]. In the presence of stoichiometric EtAlCl 2 , the (trifluoromethyl)alkenes readily eliminated F − and underwent cationic substitution with arenes to produce 3,3-difluoroallylated arenes (197)(198)(199)(200)(201)(202) in good yields. The silyl ether 202 was isolated after the quenching procedure.…”
Section: Benzylic and Allylic C-f Bonds Cleavagementioning
confidence: 99%
“…[3] Nevertheless, the fact that -CF 2 -unit finds a wide occurrence in pharmaceutically and agrochemically relevant molecules [4] evokes considerable interest from the synthetic community regarding selective C À F bond functionalization of CF 3 group. [5] In this area, the past several years have witnessed significant progress with respect to aryl-CF 3 [6][7][8][9][10] and carbonyl-CF 3 , [11] however, the alkenyl counterparts remain comparatively far less explored. Due to the competing interference of highly activated alkenyl moiety, the vast majority of reported protocols only led to g-selective defluorinative functionalization for gem-difluoroalkene synthesis.…”
mentioning
confidence: 99%