Organisch-Chemisches Institut, Westfälische Wilhelms-Universität, Corrensstrasse 40, 48149, Münster, Germany.
Angew Chem Int Ed Engl. 2021 Aug 16;60(34):18605-18611. doi: 10.1002/anie.202101689. Epub 2021 Jul 21.
Light-mediated coupling of acylsilanes with indoles is reported. This photo click reaction occurs under mild conditions (415 nm) mostly in quantitative yield and provides stable silylated N,O-acetals via light mediated siloxycarbene generation with subsequent indole-N-H insertion. We show that this very efficient and fully atom economic coupling process can be applied to conjugate complex systems, as documented by the clicking of carbohydrates with indole alkaloids. The method is also applicable to the conjugation of polymer chains. The linking acetal moiety can be readily cleaved and it is also shown that wavelength-selective coupling and cleavage with acyl silanes bearing a second photoactive moiety is possible. This is documented by a successful polymerization/depolymerization sequence and by a polymer folding/unfolding process.
报道了酰基硅烷与吲哚的光介导偶联。该光点击反应在温和条件下（415nm）发生，产率大多为定量，通过光介导硅氧基卡宾的生成以及随后的吲哚-N-H 插入，提供了稳定的硅烷基化 N,O-缩醛。我们表明，这种非常高效且完全原子经济性的偶联过程可应用于共轭复杂体系，如通过吲哚生物碱与碳水化合物的点击反应来证明。该方法也适用于聚合物链的连接。连接的缩醛部分可以很容易地断裂，并且还表明带有第二个光活性部分的酰基硅烷的波长选择性偶联和断裂是可能的。这通过成功的聚合/解聚序列和聚合物折叠/展开过程得到证明。
