School of Chemistry, Raymond and Beverly Sackler Faculty of Exact Sciences, 69978, Tel Aviv, Israel.
Department of Chemistry, Scripps Research, 10550 North Torrey Pines Road, La Jolla, CA 92037, USA.
Angew Chem Int Ed Engl. 2022 May 23;61(22):e202202187. doi: 10.1002/anie.202202187. Epub 2022 Mar 29.
Adamantyl-dioxetane luminophores are an important class of chemiluminescent molecular probes for diagnostics and imaging. We have developed a new efficient synthetic route for preparation of adamantyl-enolether as precursors for dioxetane chemiluminescent luminophores. The synthesis is convergent, using an unusual Stille cross-coupling reaction employing a stannane-enolether, to directly afford adamantyl-enolether. In a following simple step, the dioxetane is obtained by oxidation of the enolether precursor with singlet-oxygen. The scope of this synthetic route is broad since a large number of haloaryl substrates are either commercially available or easily accessible. Such a late-stage derivatization strategy simplifies the rapid exploration of novel luminogenic molecular structures in a library format and simplifies the synthesis of known dioxetane luminophores. We expect that this new synthetic strategy will be particularly useful in the design and synthesis of yet unexplored dioxetane chemiluminescent luminophores.
金刚烷基二氧杂环乙烷发光体是一类重要的化学发光分子探针，可用于诊断和成像。我们开发了一种新的有效合成方法，用于制备金刚烷基烯醚作为二氧杂环乙烷化学发光发光体的前体。该合成方法是收敛的，使用不寻常的 Stille 交叉偶联反应，采用锡烷烯醚，直接得到金刚烷基烯醚。在接下来的简单步骤中，通过单重态氧氧化烯醚前体得到二氧杂环乙烷。由于大量的卤代芳基底物要么可商购，要么容易获得，因此该合成路线的适用范围很广。这种后期衍生化策略简化了以文库格式快速探索新型发光分子结构的过程，并简化了已知二氧杂环乙烷发光体的合成。我们预计，这种新的合成策略在设计和合成尚未探索的二氧杂环乙烷化学发光发光体方面将特别有用。
