*Article* **Preparation of Chiral Enantioenriched Densely Substituted Cyclopropyl Azoles, Amines, and Ethers via Formal S***N***2***-* **Substitution of Bromocylopropanes**

**Hillary Straub 1, Pavel Ryabchuk 1,†, Marina Rubina 1,2 and Michael Rubin 1,2,\***


**Abstract:** Enantiomerically enriched cyclopropyl ethers, amines, and cyclopropylazole derivatives possessing three stereogenic carbon atoms in a small cycle are obtained via the diastereoselective, formal nucleophilic substitution of chiral, non-racemic bromocyclopropanes. The key feature of this methodology is the utilization of the chiral center of the cyclopropene intermediate, which governs the configuration of the two adjacent stereocenters that are successively installed via 1,4 addition/epimerization sequence.

**Keywords:** cyclopropenes; cyclopropanes; nucleophilic addition; metal-templated reactions
