The metal free, single amino acid-catalyzed asymmetric desymmetrization (ADS) of meso-compounds with nitrosobenzene has been investigated using DFT. In this communication, we describe the role of electrostatic and dipole-dipole interactions in amino acid-catalyzed reactions, which has not previously been invoked in discussions of these important reactions.

We report a desymmetrization of cyclohexadienones by intramolecular conjugate addition of a tethered dithiane nucleophile. Mild reaction conditions allow the formation of diversely functionalized fused bicyclic lactones. The products participate in facially selective additions from the convex surface, leading to allylic alcohol derivatives.

The asymmetric desymmetrization of 4,6-diprotected myo-inositol derivatives was achieved by using a bifunctional, readily available nucleophilic catalyst. The orthogonally protected products were obtained in 80-99% yield with 90-99% ee. Such structures serve as potential enantiopure building blocks for the synthesis of myo-inositol phosphates.

An efficient chemical synthesis of mycothiol involving the regioselective ketopinyl desymmetrization of 2,4,5,6-tetrabenzylated D-myo-inositol as the key step is described. Together with a highly α-stereoselective D-glucosaminylation, the whole procedure was accomplished in eight steps with an overall yield of 40%.

A crystalline triply bridged molecular gyroscope has been prepared and analyzed by single-crystal X-ray diffraction. A convergent synthetic strategy was developed to control the direction of the three bridges, from the preferred two zonal and one meridional arrangement of a one-step cylclization process to the directed three meridional bridges achieved by a north-south desymmetrization.

A "stop-and-flow" strategy was developed for the chemoselective dioxygenation of alkenes with a PIFA-initiated cyclization. This method is conceived for the desymmetrization of seco-diene, and a series of substituted 5-hydroxymethyl-γ-lactones were constructed after hydrolysis. This strategy also differentiates terminally substituted alkenes and constitutes a potentially novel synthetic approac...

Both enantiomers (3 and 4) of dimethyl cis-(4-acetoxycyclopent-2-enyl)malonate (3), known intermediates for the synthesis of epijasmonate, were prepared in an enantio-enriched form from common starting material 2 based on desymmetrization of the meso-character by palladium-catalyzed asymmetric allylic alkylation.

Amidase-catalyzed desymmetrization of meso-N-heterocyclic dicarboxamides under very mild conditions provided a highly efficient and practical method for the preparation of enantiomerically pure carbamoyl-substituted heterocyclic amino acids that were unique and versatile platforms for the construction of both antipodes of aza-sugar containing nucleoside analogs.