来自日本橙蝇的天然存在的 (4 R ,5 R )-4-羟基-γ-十内酯和来自收割机蛛形纲动物的 (4 S ,5 R )-4-羟基-γ-十二内酯及其立体异构体是由手性池材料d-葡萄糖酸-δ-内酯分几步合成。后者的一锅转化为γ-乙烯基-β羟基- γ内酯,交叉复分解以必要的烯烃和氢化启用的合成顺式内酯在短短的两锅操作。γ-乙烯基-β-羟基-γ-内酯的额外有效Pd催化烯丙基异构化导致高产率的抗-内酯。
A Protecting-Group-Free Synthesis of Hagen’s Gland Lactones
摘要:
A practical protecting group free synthesis of Hagen's gland lactones 1 and 2 is accomplished in four steps and 25.6 and 37.4% overall yields, respectively. The strategy relies on a one-pot conversion of D-glucono-delta-lactone to beta-hydroxy-gamma-vinyl-gamma-lactone, cross-metathesis, and iodocyclization-deiodinization as key steps.