Gold-Catalyzed 1,2-Difunctionalizations of Aminoalkynes Using Only N- and O-Containing Oxidants

We report two viable routes for the 1,2-difunctionalization of aminoalkynes using only oxidants. In the presence of a gold catalyst, nitrones enable the oxoamination of aminoalkynes 1 to form 2-aminoamides 2. With a suitable gold catalyst, nitrosobenzenes implement an alkyne/nitroso metathesis of the same substrates to give 2-oxoiminylamides 3. These two novel oxidations also provide 1,2-aminoalcohols with opposite regioselectivity via NaBH4 reduction in situ.

本研究报道了两条仅以氧化剂为试剂实现氨基炔烃（aminoalkynes）1,2-双官能团化（1,2-difunctionalization）的可行路径。在金催化剂（gold catalyst）存在时，硝酮（nitrones）可介导氨基炔烃1发生氧胺化反应，生成2-氨基酰胺（2-aminoamides）2。采用适配的金催化剂，亚硝基苯（nitrosobenzenes）可对同类底物发生炔烃/亚硝基复分解（alkyne/nitroso metathesis）反应，得到2-氧亚氨基酰胺（2-oxoiminylamides）3。上述两种新型氧化反应还可通过原位硼氢化钠（NaBH4）还原，得到区域选择性相反的1,2-氨基醇（1,2-aminoalcohols）。