Department of Chemistry and Biochemistry , University of Colorado , Boulder , Colorado 80309 , United States.
Org Lett. 2018 Apr 6;20(7):1936-1940. doi: 10.1021/acs.orglett.8b00475. Epub 2018 Mar 12.
A stereospecific cross-coupling reaction of anomeric nucleophiles with diaryliodonium triflates resulting in the synthesis of aryl C-glycosides is reported. This process capitalizes on a stereoretentive reaction of configurationally stable C1 stannanes and is promoted by a palladium catalyst in the presence of a bulky phosphine ligand that suppresses the undesired β-elimination. The utility of this reaction has been demonstrated in the preparation of a series of C-glycosides derived from common saccharides resulting in exclusive transfer of anomeric configuration from the anomeric nucleophile to the product, and in the synthesis of empagliflozin, a commercial antidiabetic drug.
报道了一种对映选择性的糖苷偶联反应，芳基碘𬭩三氟甲磺酸酯与糖苷亲核试剂反应，生成芳基 C-糖苷。该过程利用构型稳定的 C1 锡烷的立体保留反应，并在膦配体的存在下由钯催化剂促进，该配体抑制了不需要的β-消除。该反应的实用性已在一系列从常见糖衍生的 C-糖苷的制备中得到证明，结果是从糖苷亲核试剂到产物的对映构型完全转移，并且在合成抗糖尿病药物恩格列净的过程中得到了证明。
