title: Influence of alkoxy groups on rates of acetal hydrolysis and tosylate solvolysis: electrostatic stabilization of developing oxocarbenium ion intermediates and neighboring-group participation to form oxonium ions.
abstract: The hydrolysis of 4-alkoxy-substituted acetals was accelerated by about 20-fold compared to that of sterically comparable substrates that do not have an alkoxy group. Rate accelerations are largest when the two functional groups are linked by a flexible cyclic tether. When controlled for the inductive destabilization, an alkoxy group can accelerate acetal hydrolysis by up to 200-fold. The difference in rates of acetal hydrolysis between a substrate where the alkoxy group was tethered to the acetal group by a five-membered ring compared to one where it was tethered by an eight-membered ring was less than 100-fold, suggesting that fused-ring intermediates were not formed. By comparison, the difference in rates of solvolysis of structurally related tosylates were nearly 10(6)-fold between the five- and eight-membered ring series. This observation implicates neighboring-group participation in the solvolysis of tosylates but not in the hydrolysis of acetals. The acceleration of acetal hydrolysis by an alkoxy group is better explained by electrostatic stabilization of intermediates that accumulate positive charge at the acetal carbon atom.
authors: Department of Chemistry, New York University, 100 Washington Square East, New York, New York 10003, United States.
authors: Angie
authors: A
authors: Garcia
authors: Department of Chemistry, New York University, 100 Washington Square East, New York, New York 10003, United States.
authors: Douglas A L
authors: DA
authors: Otte
authors: Department of Chemistry, New York University, 100 Washington Square East, New York, New York 10003, United States.
authors: Walter A
authors: WA
authors: Salamant
authors: Department of Chemistry, New York University, 100 Washington Square East, New York, New York 10003, United States.
authors: Jillian R
authors: JR
authors: Sanzone
authors: Department of Chemistry, New York University, 100 Washington Square East, New York, New York 10003, United States.
authors: K A
authors: KA
authors: Woerpel
mesh_terms: D000080:Acetals / Q000737:chemistry*; D000438:Alcohols / Q000737:chemistry*; D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000138:chemical synthesis* / Q000737:chemistry; D006868:Hydrolysis; D007477:Ions / Q000138:chemical synthesis / Q000737:chemistry; D015394:Molecular Structure; D009861:Onium Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D012995:Solubility; D055672:Static Electricity; D014105:Tosyl Compounds / Q000737:chemistry*
chemical_list: D000080:Acetals; D000438:Alcohols; D019086:Bridged Bicyclo Compounds, Heterocyclic; D007477:Ions; D009861:Onium Compounds; D014105:Tosyl Compounds; C059688:alkoxyl radical