Bent Bond/Antiperiplanar Hypothesis: Modulating the Reactivity and the Selectivity in the Glycosylation of Bicyclic Pyranoside Models.

Glycosylation reactions were performed on a series of bicyclic C2-substituted pyranoside models to isolate and analyze factors that control the glycosylation stereoselectivities observed in carbohydrates. The bent bond/antiperiplanar hypothesis (BBAH) orbital model rationalizes all of these results by considering hyperconjugation interactions between groups at C2 and the two τ bonds (bent bonds) of oxocarbenium ion intermediates formed under the glycosylation conditions. According to the BBAH, nucleophiles add to oxocarbenium intermediates by SN2-like antiperiplanar displacement of the weaker of their two τ bonds.

Applying the Bent Bond/Antiperiplanar Hypothesis to the Stereoselective Glycosylation of Bicyclic Furanosides.

The glycosylation stereoselectivities for a series of bicyclic furanoside models have been carried out in the presence of weak nucleophiles. These results were analyzed through the bent bond/antiperiplanar hypothesis (BBAH) orbital model to test its validity. According to the BBAH, incoming nucleophiles displace one of the two bent bonds of bicyclic oxocarbenium ion intermediates in an antiperiplanar fashion. The glycosylation stereoselectivity is then governed by the displacement of the weaker bent bond as determined by the presence of electron-withdrawing or -donating substituents at C2. Overall, the BBAH analysis expands Woerpel's "inside/outside attack" glycosylation model by considering the stereoelectronic influence of neighboring electron-withdrawing and -donating groups on the nucleophilic addition to oxocarbenium ion intermediates.

High-Temperature Isomerization of Benzenoid Polycyclic Aromatic Hydrocarbons. Analysis through the Bent Bond and Antiperiplanar Hypothesis Orbital Model.

L. T. Scott has discovered the 1,2-swapping of carbon and hydrogen atoms which is known to take place on benzenoid aromatics (up to ∼1000 °C range). For example, 13C-1-naphthalene is specifically converted to 13C-2-naphthalene, and there is evidence that this occurs through the formation of benzofulvene and a naphthalene-carbene intermediate. Application of the bent bond/antiperiplanar hypothesis leads to the postulate that higher in energy pyramidal singlet diradical intermediates can be used to propose a mechanism that rationalizes various atom rearrangements on benzenoid aromatics and related isomeric compounds.

Bent bonds (τ) and the antiperiplanar hypothesis, and the reactivity at the anomeric center in pyranosides.

The stereoselectivity of nucleophilic addition on oxocarbenium ions derived from the bicyclic pyranoside model with or without a C2-OR group can be understood through the use of the bent-bond and the antiperiplanar hypothesis in conjunction with the concept of hyperconjugation as an alternative interpretive model of structure and reactivity.

Evaluation of the effect of fluorination on the property of monofluorinated dimyristoylphosphatidylcholines.

The synthesis of three monofluorinated dimyristoylphosphatidylcholines (F-DMPC's), with the fluorine atom located at the extremities of the acyl chain in position 2 of the glycerol (sn-2), is described. The synthetic strategy relies on the coupling of 1-myristoyl-2-hydroxy-sn-glycero-3-phosphocholine (14:0 lyso-PC) and three different fluorinated fatty acids. FTIR results suggest that the presence of the fluorine atom does not significantly perturb the lipid phase transition temperature and conformational order even though a small increase in the phase transition temperature is observed for the 14F derivative. Overall, comparison with previously reported F-DMPC's where the fluorine atom is located in the middle or close from either side supports the fact that monofluorination of the acyl chain in sn-2 brings minimal perturbation to the lipid bilayer. F-DMPC's could therefore potentially be used as NMR probes for the investigation at the molecular level of the interaction between drugs or peptides and lipid membranes and for the study of membrane topology.