Radical Cations

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Key Points Primary Fate of Radical Cations � A radical cation will be generated from the electrophore on the molecule with the lowest oxidation potential (usually π or n, where n = nonbonding electrons). � The chemistry of the resultant radical cation is determined from the functionality around its periphery. � Deprotonation of the radical cation is a major pathway, resulting in a radical which adheres to typical radical reactivity patterns. � Secondary reactions play a major role in our generation and use of radical cations. Schmittle, M.; Burghart, A. Angew. Chem. Int. Ed. Engl. 1997, 36, 2550.
Primary Fate of Radical Cations Symbol Classification Primary Product A B CH C–H deprotonation π-C • + H + or n-C • + H + C H AH A–H deprotonation π-A • + H + O, N, S, X H AB A–B bond cleavage π-A • + B + or π-A + + B • A B CC C–C bond cleavage π-C • + C + C C CX C–X bond cleavage π-C • + X + C Si, Sn Nu Nu attack Nu-π-A-B •+ A B CA cycloaddition cycloaddition A B R rearrangement rearrangement A B ET electron transfer π-A-B or π-A-B 2+ A B Rad radical attack R-π-A-B + A B RA radical anion attack RA-π-A-B A B H hydrogen transfer H-π-A-B + A B Dim dimerization (π-A-B) 2 2+ A B Schmittle, M.; Burghart, A. Angew. Chem. Int. Ed. Engl. 1997, 36, 2550.
Page 1 and 2: Radical Cations •+ : Generation,
Page 3 and 4: � Stoichiometric oxidant: SET Bn
Page 5: � Anodic oxidation MeO N H N CO 2
Page 9 and 10: Thermochemical Cycle: Calculating p
Page 11 and 12: Me Ph Ph O Ph O Ph O Deprotonation
Page 13 and 14: π-RH •+ Deprotonation � π-RH
Page 15 and 16: n-RH •+ Deprotonation � n-RH
Page 17 and 18: σ-CH •+ Deprotonation � Deprot
Page 19 and 20: π-AH •+ Deprotonation � π-OH
Page 21 and 22: � Reaction at the ortho-position
Page 23 and 24: Primary Fate of Radical Cations Sym
Page 25 and 26: π-A-B •+ Bond Dissociation � C
Page 27 and 28: � Limited mostly to azoalkanes an
Page 29 and 30: π-C-C •+ Bond Dissociation � F
Page 31 and 32: π-C-C •+ Bond Dissociation � N
Page 33 and 34: n-C-C •+ Bond Dissociation � To
Page 35 and 36: Me 3SiO σ-C-C •+ Bond Dissociati
Page 37 and 38: π-C-X •+ Bond Dissociation: Calc
Page 39 and 40: π-C-X •+ Bond Dissociation � R
Page 41 and 42: � “Cation pool” oxidizes benz
Page 43 and 44: Me 3Si � Stronger oxidant than im
Page 45 and 46: ClO 4 - N Me NC Ph CN σ-C-X •+ B
Page 47 and 48: � Moeller en route to (-)-alliaco
Page 49 and 50: N PTOC PTOC = Nu-n-A-B •+ AcOH N
Page 51 and 52: Primary Fate of Radical Cations Sym
Page 53 and 54: Diels-Alder [4 + 2] Cycloaddition
Page 55 and 56: � Photoredox catalyzed radical ca
Page 57 and 58:
Primary Fate of Radical Cations Sym
Page 59 and 60:
Primary Fate of Radical Cations �
Page 61 and 62:
� The Hofmann-Löffler-Freytag re
Page 63 and 64:
� Epoxonium cyclization Bn O OMe
Page 65:
H H H O R !-arylation O intramolecu
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Radical Cations

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