Department of Chemistry, University of Toronto, 80 St George St, Toronto, Ontario, Canada M5S 3H6.
Dalton Trans. 2018 Jul 10;47(27):8933-8939. doi: 10.1039/c8dt01717d.
Phosphine oxidation by MesCNO is rapid; however, an FLP strategy intercepts the 1,3 addition products including [MesC(R3P)NOB(C6F5)3] (R = Ph 1, p-tol 2), [MesC(Mes2PH)NOB(C6F5)3] 3 (MesC(NOB(C6F5)3)Ph2P)2(CH2)n (n = 2: 4, 3: 5) and [MesC(Ph3P)NOB(C6F4H)3] 6. These species are shown to react with tBuOK or [Bu4N]F permitting the oxidation to proceed via a process involving borane dissociation. Similarly, the equilibrium established by 1 with B(C6F4H)3 and 6 with B(C6F5)3 provides experimental support for the "Cummins mechanism" for these phosphine oxidations.
MesCNO 对膦的氧化作用迅速；然而，FLP 策略可以拦截包括 [MesC(R3P)NOB(C6F5)3]（R = Ph 1，p-tol 2）、[MesC(Mes2PH)NOB(C6F5)3] 3（MesC(NOB(C6F5)3)Ph2P)2(CH2)n（n = 2：4，3：5）和 [MesC(Ph3P)NOB(C6F4H)3] 6 的 1,3 添加产物。这些物质被证明可与 tBuOK 或 [Bu4N]F 反应，从而使氧化反应通过涉及硼烷解离的过程进行。同样，化合物 1 与 B(C6F4H)3 和化合物 6 与 B(C6F5)3 之间建立的平衡为这些膦的氧化反应的“Cummins 机制”提供了实验支持。
