Institute of Chemistry, Department of Organic and Bioorganic Chemistry, University of Graz, NAWI Graz, BioTechMed Graz, Field of Excellence BioHealth, Heinrichstraße 28, 8010, Graz, Austria.
Angew Chem Int Ed Engl. 2022 Apr 19;61(17):e202117103. doi: 10.1002/anie.202117103. Epub 2022 Mar 4.
The concurrent operation of chemical and biocatalytic reactions in one pot is still a challenging task, and, in particular for chemical photocatalysts, examples besides simple cofactor recycling systems are rare. However, especially due to the complementary chemistry that the two fields of catalysis promote, their combination in one pot has the potential to unlock intriguing, unprecedented overall reactivities. Herein we demonstrate a concurrent biocatalytic reduction and photocatalytic oxidation process. Specifically, the enantioselective biocatalytic sulfoxide reduction using (S)-selective methionine sulfoxide reductases was coupled to an unselective light-dependent sulfoxidation. Protochlorophyllide was established as a new green photocatalyst for the sulfoxidation. Overall, a cyclic deracemization process to produce nonracemic sulfoxides was achieved and the target compounds were obtained with excellent conversions (up to 91 %) and superb optical purity (>99 % ee).
一锅法中同时进行化学和生物催化反应仍然是一项具有挑战性的任务，特别是对于化学光催化剂而言，除了简单的辅因子回收系统之外，这种例子很少见。然而，由于这两个催化领域促进的互补化学，它们在一锅法中的结合有可能释放出有趣的、前所未有的整体反应性。在此，我们展示了一个同时进行的生物催化还原和光催化氧化过程。具体而言，使用（S）-选择性甲硫氨酸亚砜还原酶的对映选择性生物催化亚砜还原与非选择性依赖光的亚砜氧化偶联。原叶绿素被确定为用于亚砜氧化的新型绿色光催化剂。总的来说，实现了一种环状外消旋化过程以生产非外消旋的亚砜，并且目标化合物的转化率高达 91%（最高）和极好的光学纯度（>99%ee）。
