| This work summarizes the history of anchimeric assistance, from the early discoveries by Saul Winstein to their repercussions on the study of the chemistry of amines, ethers and sulfides containing an α to ϵ halide. We present a brief survey of trends and techniques available for the diagnostics of anchimeric assistance.; We have investigated the effect of anchimeric assistance by sulfur, nitrogen and oxygen on the electrophilic behavior of β-halogens in a family of mustard compounds derived from 1,5-cyclooctadiene and in a series of pinol derivatives.; We have developed a novel synthesis of 2,6-dichloro-9-thiabicyclo[3.3.1]nonane (61) from 1,5-cyclooctadiene, and we have investigated in depth the chemistry of this compound. We present our studies on the electrophilic behavior of 61 towards a variety of nucleophiles, how it is influenced by the oxidation state of the central sulfur, on the asymmetry of 61 and its reactivity towards Grignard reagents, which allowed the synthesis of conformationally rigid structures.; We have optimized the synthesis of 2,6-dichloro-9-azabicyclo[3.3.1]nonane (2) starting from 1,5-cyclooctadiene, greatly extending its scope and allowing the synthesis of numerous derivatives of 131 carrying a different substituent on the central nitrogen. The electrophilic behavior of 131 has also been investigated, indicating a high activation towards nucleophilic displacement of the halides to yield C2-symmetric structures.; Finally, a series of derivatives of pinol were synthesized and explored as possible scaffolds for the synthesis of libraries. |
