Fürst-Plattner rule

The Fürst-Plattner rule (also known as the trans-diaxial effect) describes the stereoselective addition of nucleophiles to cyclohexene derivatives.

Cyclohexene derivatives, such as imines, epoxides, and halonium ions, react with nucleophiles in a stereoselective fashion, affording trans-diaxial addition products. The term “Trans-diaxial addition” describes the mechanism of the addition, however the products are likely to equilibrate by ring flip to the lower energy conformer, placing the new substituents in the equatorial position.

Epoxidation of a substituted cyclohexene affords a product where the R group resides in the pseudo-equatorial position. Nucleophilic opening of this epoxide can occur by attack at either the 1 or 2 position. The major product forms from attack at the 1 position, due to the instability of the twist boat product formed by addition at the 2 position (disfavored by approximately 5 kcal/mol). Similarly, the Fürst-Plattner rule applies to nucleophilic additions to imines and halonium ions.

A recent example of the Fürst-Plattner rule can be seen from Chrisman et al. where limonene is epoxidized to give a 1:1 mixture of diastereomers. Exposure to a nitrogen nucleophile in water at reflux provides only one ring opened product in 75-85% ee.

The half-chair conformation indicates that attack occurs stereoselectively on the diastereomer where the electrophilic carbon can receive the nucleophile and proceed to the favored chair conformation.

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