Institut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 115, 10623, Berlin, Germany.
Angew Chem Int Ed Engl. 2017 Mar 13;56(12):3389-3391. doi: 10.1002/anie.201611813. Epub 2017 Feb 9.
Catalytic C(sp )-O bond cleavage promoted by B(C F ) /Et SiH proceeds preferentially with primary tosylates in the presence of primary and secondary silyl ethers and aryl ethers. This reactivity difference enables the chemoselective defunctionalization of several 1,n-diols, and the efficiency of the new procedure is highlighted by the selective deoxygenation of the hydroxymethyl group of an orthogonally protected carbohydrate. Tosylates with an adjacent phenyl group are cleaved with anchimeric assistance.
B(C F ) /三乙基硅烷促进的催化 C(sp )-O 键断裂在伯和仲硅醚以及芳基醚存在的情况下优先与伯对甲苯磺酸盐反应。这种反应性差异使得几种 1,n-二醇能够选择性去官能化，并且新方法的效率通过邻位保护的碳水化合物的羟甲基的选择性脱氧得到了突出体现。具有相邻苯基的对甲苯磺酸盐在助催化剂的帮助下发生断裂。
