Department of Environmental Science, Graduate School of Fisheries and Environmental Sciences, Nagasaki University.
Graduate School of Engineering, Nagasaki University.
Chem Pharm Bull (Tokyo). 2022;70(9):599-604. doi: 10.1248/cpb.c22-00049.
1,1'-Bi-2-naphthol (BINOL)-derived chiral bifunctional sulfide and selenide catalysts that possess a hydroxy group are known to be effective catalysts for enantioselective bromolactonizations. When applied to asymmetric iodolactonizations of 4-pentenoic acids, these catalysts yield chiral γ-butyrolactone products that are important compounds in medicinal chemistry. Although chiral bifunctional selenides have shown good catalytic performances in enantioselective iodolactonizations, reactions with BINOL-derived chiral sulfide catalysts unexpectedly gave iodolactonization products in nearly racemic forms. The roles of chalcogenide moieties and hydroxy groups on bifunctional catalysts were investigated, and the importance of both a selenide moiety and a hydroxy group on chiral bifunctional selenide catalysts to achieve enantioselective iodolactonizations was clarified. An optimized chiral bifunctional selenide catalyst was applied to the asymmetric synthesis of chiral γ-butyrolactones and phthalides. Furthermore, the utility of chiral bifunctional selenides was also demonstrated in the catalytic enantioselective desymmetrizing iodolactonization of α,α-diallyl carboxylic acids.
1,1'-联萘酚（BINOL）衍生的手性双功能硫化物和硒化物催化剂，具有羟基，被认为是对映选择性溴内酯化的有效催化剂。当应用于 4-戊烯酸的不对称碘内酯化时，这些催化剂生成手性 γ-丁内酯产物，这些产物是药物化学中的重要化合物。尽管手性双功能硒化物在对映选择性碘内酯化中表现出良好的催化性能，但与 BINOL 衍生的手性硫化物催化剂的反应出人意料地以近外消旋形式得到碘内酯化产物。研究了硫属元素部分和双功能催化剂上羟基的作用，阐明了手性双功能硒化物催化剂上硒化物部分和羟基对实现对映选择性碘内酯化的重要性。优化的手性双功能硒化物催化剂被应用于手性 γ-丁内酯和邻苯二甲酸内酯的不对称合成。此外，手性双功能硒化物的用途还在α,α-二烯丙基羧酸的催化对映选择性去对称碘内酯化中得到了证明。
