Substituted Diazatetracyclo[4.4.0.13,10.15,8]dodecanes as Stable Caged Proton Sponges
| Authors | |
|---|---|
| Year of publication | 2012 |
| Type | Article in Periodical |
| Magazine / Source | The Journal of Organic Chemistry |
| MU Faculty or unit | |
| Citation | |
| Web | http://pubs.acs.org/doi/abs/10.1021/jo202235f |
| Doi | http://dx.doi.org/10.1021/jo202235f |
| Field | Organic chemistry |
| Keywords | transprotonation - basicity - proton sponge - DTDs |
| Description | Herein, we report a molecular framework design differing significantly from the traditional topology of proton sponges. We developed a synthetic approach to the preparation of caged secondary amines by acid-catalyzed rearrangement of fused tetracyclic heterocycles synthesized by intramolecular criss-cross cycloaddition. Alkylation of amines led to air nonsensitive diazatetracyclo[4.4.0.13,10.15,8]dodecanes (DTDs) with rare alicyclic scaffolding in high overall yields. Their pKBH+ values were determined by transprotonation experiments as well as their sensitivity toward nucleophiles, acids and bases. Crystal structures of free base and monoprotonated form are discussed. |
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