2018
DOI: 10.1021/jacs.8b05935
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Mechanism and Origins of Chemo- and Stereoselectivities of Aryl Iodide-Catalyzed Asymmetric Difluorinations of β-Substituted Styrenes

Abstract: The mechanism of the aryl iodide-catalyzed asymmetric migratory geminal difluorination of β-substituted styrenes (Banik et al. Science 2016, 353, 51) has been explored with density functional theory computations. The computed mechanism consists of (a) activation of iodoarene difluoride (ArIF2), (b) enantiodetermining 1, 2-fluoroiodination, (c) bridging phenonium ion formation via SN2 reductive displacement, and (d) regioselective fluoride addition. According to the computational model, the ArIF2 intermediate i… Show more

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Cited by 100 publications
(63 citation statements)
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“…We wish to convey that locating various transition state geometries in hypercoordinate iodine catalyzed reactions could be challenging due to geometry convergence issues. Similar computational methods to those employed in this study have successfully been employed in recent studies of hypercoordinate iodine reactions 19…”
Section: Methodsmentioning
confidence: 99%
“…We wish to convey that locating various transition state geometries in hypercoordinate iodine catalyzed reactions could be challenging due to geometry convergence issues. Similar computational methods to those employed in this study have successfully been employed in recent studies of hypercoordinate iodine reactions 19…”
Section: Methodsmentioning
confidence: 99%
“…Thep rimary amide catalyst (Table 1, entry 7) displayed similar activity,w hereas dimethylation (Table 1, entry 8) caused anotable drop in e.r. To explore the possible involvement of non-covalent aromatic interactions in catalysis, [27] the peripheral substituent Rw as replaced by ac yclohexyl motif (Table 1, entry 9). This proved to be highly detrimental to efficiency (47 %y ield versus 72 %).…”
mentioning
confidence: 99%
“…The next step of the cycle is the loss of a fluoride from ( R , R ) -1c-F 2 to yield the cationic fluoroiodonium active catalytic species Int1 . Similar to the mechanism proposed by Jacobsen, Xue, and Houk for the aryl iodine-catalyzed asymmetric difluorination of β-substituted styrenes, 62 we employed two molecules of HF as an activation model for the iodoarene difluoride. Coordination of the two HF molecules results in the formation of the hydrogen-bonded difluoride complex ( R , R ) -1c-F 2 -2HF , which is 0.6 kcal/mol lower than ( R , R ) -1c-F 2 .…”
Section: Resultsmentioning
confidence: 99%