John Gilbert


BS, University of Wyoming, 1961
MS, Yale University, 1962
Yale University, PhD, 1965

Physical organic chemistry

Our research interests encompass a wide range of problems, including computational, physical organic, and synthetic organic chemistry. Among the topics of current emphasis is the development of theoretical and experimental approaches to define the nature of strained cycloalkynes. We have gathered evidence suggesting that these systems react as though the triple bond were better represented as a dicarbene, that is, a molecule having vicinal carbene centers. The interesting ramifications of this property are being explored in a variety of cycloalkynes and arynes. The possibility that the latter react as dicarbenes is particularly fascinating in that rationalizations of their pericyclic chemistry have rested on their reacting as diradicals. Another area of research involves the development of synthetic approaches to biologically active terpenoids. Previous efforts in this area have led to a convergent enantioselective synthesis of the trichothecene skeleton, which characterizes a number of fungal metabolites. Elaboration of this approach is expected to provide useful analogs having significant pharmacological activities. Molecular modeling is used to design target molecules, and such modeling is also a factor in a related research initiative in my group, the synthesis of biologically active anti-oxidants.

Representative Publications