Catalytic Asymmetric [4 + 2] Cycloadditions and Hosomi–Sakurai Reactions of α‑Alkylidene β‑Keto Imides

Highly enantioselective catalytic asymmetric reactions of rationally designed α-alkylidene β-keto imides are described. The [4 + 2] cycloadditions and Hosomi–Sakurai reactions of α-alkylidene β-keto imides proceed with high enantioselectivity and yield. The [4 + 2] cycloadditions of the imides with various dienes afford products bearing an all-carbon quaternary stereogenic center at the ring junction. α-Alkylidene β-keto imides should be useful for the enantioselective total synthesis of natural products and other catalytic asymmetric applications.

本描述详尽阐释了经过理性设计的α-烷基亚甲基β-酮亚胺在催化不对称反应中的高对映选择性。α-烷基亚甲基β-酮亚胺的[4 + 2]环加成反应以及Hosomi-Sakurai反应均展现出卓越的对映选择性和产率。与多种二烯的[4 + 2]环加成反应能够生成在环连接处含有全碳四价立体中心的产物。α-烷基亚甲基β-酮亚胺有望在天然产物的对映选择性全合成及其他催化不对称应用中发挥重要作用。