Institute of Organic Chemistry & MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, Sun Yat-Sen University, Guangzhou, 510275, China.
Angew Chem Int Ed Engl. 2019 Jan 28;58(5):1315-1319. doi: 10.1002/anie.201811621. Epub 2019 Jan 9.
An unprecendented chiral sulfide catalyzed desymmetrizing enantioselective chlorination is disclosed. Various aryl-tethered diolefins and diaryl-tethered olefins afforded teralins and tricyclic hexahydrophenalene derivatives, respectively, bearing multiple stereogenic centers in high yields with excellent enantio- and diastereoselectivities. In contrast, the tertiary amine catalyst (DHQD) PHAL led to a diastereomeric product. The products could be transformed into a variety of compounds, such as spiro-N-heterocycles.
本研究揭示了一种前所未有的手性硫醚催化的去对称对映选择性氯化反应。各种芳基桥联二烯烃和二芳基桥联烯烃分别以高产率和优异的对映选择性和非对映选择性得到了四氢萘衍生物和三环己基六氢苯并呋喃衍生物，这些产物中含有多个手性中心。相比之下，叔胺催化剂（DHQD）PHAL 则得到了非对映异构体产物。这些产物可以转化为各种化合物，例如螺-N-杂环化合物。
