Acid/base catalysis by pure water: the aldol reaction.
[reaction: see text] The mechanism of aldol reactions in pure water has been studied with density functional calculations (B3LYP/6-311++G(3d,3p)//B3LYP/6-31G(d)). The reaction is a three-step process that involves: (1) water autoionization generates catalytic hydroxide and hydronium ions, (2) hydroxide and hydronium ions rapidly convert donor aldehyde or ketone into enol, and (3) C-C bond formation and proton transfer occur to give the aldol product. This study provides a general basis for understanding acid/base catalysis by pure water.
Zhang
Xiyun
X
Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, USA.
Houk
K N
KN
D000447:Aldehydes / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D018360:Crystallography, X-Ray; D006878:Hydroxides / Q000737:chemistry*; D007659:Ketones / Q000138:chemical synthesis* / Q000737:chemistry; D008956:Models, Chemical; D008958:Models, Molecular; D015394:Molecular Structure; D009861:Onium Compounds / Q000737:chemistry*; D013237:Stereoisomerism; D014867:Water / Q000737:chemistry
D000447:Aldehydes; D006878:Hydroxides; D007659:Ketones; D009861:Onium Compounds; D014867:Water; C027727:hydronium ion; C031356:hydroxide ion