Transition state structure for the intramolecular catalysis by carboxylate of phenyl hydrogen malonate hydrolysis

✍ Scribed by K.S. Venkatasubban; John L. Hogg

• Book ID: 104237948
• Publisher: Elsevier Science
• Year: 1979
• Tongue: French
• Weight: 193 KB
• Volume: 20
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(01)86587-4

✦ Synopsis

The intmmoZecuZm cataZysis by carboxyZ&e of pheny2 hydrogen ndonate hydrolysis has been showa to involve a sin@!e water moledle in a d-membered ring transition state.

The question of the structural requirements for intramolecular proton transfers has received considerable attention. Gandour has presented a hypothesis which predicts when intramolecular proton transfer will most likely occur:! He suggested that "the highest probability for intramolecular proton transfer will occur when the cyclic transition state formed can accomodate a linear arrangement of donor-proton-acceptor of appropriate length. This most easily occurs when the ring size is eight." We wish to report that this prediction does not hold for the intramolecular catalysis by carboxylate ion of phenyl hydrogen malonate hydrolysis. This is in apparent contrast to the many examples cited by Gandour.