Modular and Stereoselective Synthesis of C‑Aryl Glycosides via Catellani Reaction

In
this work, we describe a Catellani-type C–H glycosylation
to provide rapid access to various highly decorated α-C-(hetero)­aryl
glycosides in a modular and stereoselective manner (>90 examples).
The termination step is flexible, which is demonstrated by ipso-Heck reaction, hydrogenation, Suzuki coupling, and
Sonogashira coupling. Application of this methodology has been showcased
by preparing glycoside–pharmacophore conjugates and a dapagliflozin
analogue. Notably, the technology developed herein represents an unprecedented
example of Catellani-type alkylation involving an SN1 pathway.