Davenport Chemical Laboratories, Department of Chemistry, University of Toronto, 80 St. George St., Toronto, Ontario, M5S 3H6, Canada.
Angew Chem Int Ed Engl. 2021 Sep 20;60(39):21189-21194. doi: 10.1002/anie.202105562. Epub 2021 Aug 18.
Enantioenriched spiro-oxiranes bearing three contiguous stereocenters were synthesized using a rhodium-catalyzed asymmetric addition/aldol/spirocyclization sequence. Starting from a linear substrate, the cascade enabled the formation of a spirocyclic framework in a single step. sp - and sp-hybridized carbon nucleophiles were found to be competent initiators for this cascade, giving arylated or alkynylated products, respectively. Derivatization studies demonstrated the synthetic versatility of both the epoxide and the alkyne moieties of the products. DFT calculations were used to reconcile spectroscopic discrepancies observed between the solution- and solid-state structures of the products.
使用铑催化的不对称加成/羟醛缩合/螺环化序列合成了具有三个连续手性中心的对映富集螺环环氧乙烷。从线性底物开始，级联反应能够在一步中形成螺环骨架。发现 sp-和 sp-杂化碳亲核试剂是此级联反应的有效引发剂，分别得到芳基化或炔基化产物。衍生化研究证明了产物中环氧化物和炔烃部分的合成多功能性。DFT 计算用于调和产物在溶液和固态结构之间观察到的光谱差异。
