A new palladium-catalyzed asymmetric addition reaction of indoles to alkoxyallenes is reported. Remarkably, the reaction showed complete regioselectivity toward the nitrogen. A new mechanism distinct from that of conventional π-allyl chemistry is proposed to explain this unique selectivity. The utility of the reaction is demonstrated by highly efficient and flexible synthesis of N-glycosylindoles.

Catalytic asymmetric synthesis of N-heterocyclic glycosides free of protecting and directing groups is reported. The key reaction is highlighted by the atom-efficient and regioselective addition of unprotected pyrimidines to highly functionalized alkoxyallene. Numerous acyclic and cyclic N-heterocyclic glycosides are accessed with minimal formation of organic byproducts. The synthetic utility of the reaction is demonstrated by the first catalytic asymmetric synthesis of anticancer pharmaceutical (-)-Tegafur and stereoselective synthesis of an oxepane nucleoside derivative.

We report sequential metal catalysis towards indolocarbazole glycosides. The signature event is highlighted by i) Pd0‐catalyzed addition of indolocarbazole to alkoxyallene combined with ring‐closing‐metathesis; ii) Ru‐catalyzed chemoselective olefin migration; iii) PdII‐catalyzed oxidative cyclization to build the bicyclic core structure of the target compounds. This approach gave access to both natural pyranose‐ and non‐natural septanose glycosides. A short formal synthesis of 7‐oxostaurosporine was achieved via this strategy.

We report sequential metal catalysis towards indolocarbazole glycosides. The signature event is highlighted by i) Pd0‐catalyzed addition of indolocarbazole to alkoxyallene combined with ring‐closing‐metathesis; ii) Ru‐catalyzed chemoselective olefin migration; iii) PdII‐catalyzed oxidative cyclization to build the bicyclic core structure of the target compounds. This approach gave access to both natural pyranose‐ and non‐natural septanose glycosides. A short formal synthesis of 7‐oxostaurosporine was achieved via this strategy.

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