Neighboring group participation in organic redox reactions. 11. Anchimeric assistance by the carboxylate anion in aqueous iodine oxidations of 3-(alkylthio)propanoates

1986 ◽  
Vol 51 (7) ◽  
pp. 1026-1029 ◽  
Author(s):  
Joyce Takahashi Doi ◽  
Marvin H. Goodrow ◽  
W. Kenneth Musker
Keyword(s):  
Redox Reactions ◽  
Carboxylate Anion ◽  
Neighboring Group ◽  
Group Participation ◽  
Anchimeric Assistance ◽  
Neighboring Group Participation

Revisiting the ‘Phenonium Phenomenon’: Regiodivergent Opening of Nonsymmetrical Phenonium Ions with Halide Nucleophiles

Synlett ◽  
2020 ◽  
Vol 32 (01) ◽  
pp. 01-06
Author(s):  
Nicholas J. Race ◽  
Hannah M. Holst ◽  
Shelby B. McGuire
Keyword(s):  
Reactive Intermediates ◽  
Building Blocks ◽  
Stereospecific Synthesis ◽  
Neighboring Group ◽  
Group Participation ◽  
Physical Organic ◽  
Anchimeric Assistance ◽  
Neighboring Group Participation

Formation of phenonium ions through anchimeric assistance (neighboring-group participation) of aryl rings has been known since 1949. Although these reactive intermediates have been studied extensively by physical organic chemists, their potential as control elements in synthesis is underutilized. Presented here are our laboratory’s recently reported first examples of regiodivergent openings of nonsymmetrical phenonium ions with chloride nucleophiles. The selectivity of these processes is under reagent control. The reactions are operationally simple and permit the stereospecific synthesis of complex chiral building blocks from readily accessible epoxide starting materials.1 Introduction2 Select Examples of Phenonium Ion Methodology3 Regiodivergent Opening of Nonsymmetrical Phenonium Ions4 Summary and Outlook

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