Asymmetric synthesis in a Norrish type II cleavage reaction induced by crystal chirality.

Moderate to high enantiomeric excesses for the cis and trans olefinic products of a Norrish type II cleavage reaction have been obtained for the first time through the use of the solid-state ionic chiral auxiliary approach.

Thermal and photochemical transformation of conformational chirality into configurational chirality in the crystalline state.

Because they crystallize in chiral conformations in which abstraction of only one of two diastereotopic gamma-hydrogen atoms is possible, salts formed between achiral keto-acids possessing the tricyclo[4.4.1.0]undecane ring system and optically pure amines undergo Norrish type II cleavage in the solid state in enantiomeric excesses as high as 95% at 98% conversion, following removal of the ionic chiral auxiliaries. Thermal enolene rearrangement of the same salts results in optical yields approximately half those observed for the photochemical reaction.

Use of chirally modified zeolites and crystals in photochemical asymmetric synthesis.

Three different approaches to asymmetric induction in the cis-to-trans photoisomerization of a number of 1-benzoyl-2,3-diphenylcyclopropane derivatives are reported: the use of chiral inductors and covalent chiral auxiliaries in MY zeolites and the use of ionic chiral auxiliaries in crystals. High levels of asymmetric induction were achieved using the latter two methods-up to 71% through the use of covalent chiral auxiliaries in zeolites and a remarkable 99% via the solid state ionic chiral auxiliary approach. In the zeolite method, the diastereomeric excess was found to depend strongly on the nature of the zeolite cation, M(+), and in the ionic chiral auxiliary approach, evidence is presented that it is the fixed orientation of the benzoyl group with respect to the cyclopropane ring that controls enantioselectivity in the crystalline state-a finding that is directly relevant to theoretical work on this topic.