Far Away from Flatland. Synthesis and Molecular Structure of Dihetera[3.3.]propellanes and Trihetera[3.3.]propellanes: Advanced Analogues of Morpholine/Piperazine.

An approach to di- and trihetera[3.3.]propellanes ( = 2-4 ), advanced morpholine and piperazine analogues, is developed.

Enantioselective Synthesis of Cyclohepta[]indoles via Pd-Catalyzed Cyclopropane C(sp)-H Activation as a Key Step.

An enantioselective synthesis of functionalized cyclohepta[]indoles via Pd-catalyzed cyclopropane C-H activation followed by olefination and indole-vinylcyclopropane rearrangement is reported. The design of the chiral cyclopropane precursor was such that both enantiomeric cyclohepta[]indoles were accessed from a single compound exhibiting a "hidden" symmetry plane. The scope of the method was demonstrated by varying the substituents on the cyclopropane as well as on the heterocycle itself.

Scalable Synthesis of Biologically Relevant Spirocyclic Pyrrolidines.

Synthetic approaches toward multigram preparation of spirocyclic α,α-disubstituted pyrrolidines from readily available starting materials are discussed. It was shown that although a number of synthetic methodologies have been known to date, many of the title compounds remain hardly accessible. The most appropriate literature method (which relied on reaction of imines and allyl magnesium halide, followed by bromocyclization) was identified and optimized.