A cycle for organic nitrile synthesis via dinitrogen cleavage
A cycle for organic nitrile synthesis via dinitrogen cleavage
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DOI：
10.1021/ja066090a
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发表时间：
2006-11-01
影响因子：
15
通讯作者：
Cummins, Christopher C.
中科院分区：
文献类型：
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作者：
Curley, John J.;Sceats, Emma L.;Cummins, Christopher C.
在NaH存在下，N2与Mo(N[t-Bu]Ar)3(Ar=3，5-C6H3Me2)在室温下反应生成NMO(N[t-Bu]Ar)3(95%)。Lewis酸性三氟硅酸盐(Me_3SiOTf+吡啶或(i-Pr)_3SiOTf)催化酸性氯化物与NMO(N[t-Bu]Ar)3反应生成酰亚胺[RC(O)NMO(N[t-Bu]Ar)3][OTf](R=Me，92%；Ph，75%；t-Bu，%)。[Rc(O)NMO(N[t-Bu]Ar)3][OTf]经Me_3SiOTf处理后得到钼基硫化物R(Me_3SiO)CNMo(N[t-Bu]Ar)_3(R=Me，82%；Ph，77%；t-Bu，46%)。将R(Me3SiO)CNMo(N[t-Bu]Ar)3暴露于SnCl2或ZnCl2，生成ClMo(N[t-Bu]Ar)3(SnCl2的71−为93%)和RCN(97−99%)。金属镁将ClMo(N[t-Bu]Ar)3还原为Mo(N[t-Bu]Ar)3(74%)，完成一个合成循环。在一条新的氮衍生物路线的背景下，提出了空间受阻氮化物的官能化和从d2ketimide中挤出丁腈的新策略。
In the presence of NaH, the reaction between N2and Mo(N[t-Bu]Ar)3(Ar = 3,5-C6H3Me2) proceeds at room temperature to afford NMo(N[t-Bu]Ar)3(95%). Lewis acidic silyl triflates (Me3SiOTf + pyridine or (i-Pr)3SiOTf) mediate a reaction between acid chlorides and NMo(N[t-Bu]Ar)3to yield acyl imidos [RC(O)NMo(N[t-Bu]Ar)3][OTf] (R = Me, 92%; Ph, 75%;t-Bu, 64%). The reduction of [RC(O)NMo(N[t-Bu]Ar)3][OTf] by magnesium anthracene followed by treatment with Me3SiOTf affords molybdenum ketimides, R(Me3SiO)CNMo(N[t-Bu]Ar)3(R = Me, 82%; Ph, 77%;t-Bu, 46%). Exposing R(Me3SiO)CNMo(N[t-Bu]Ar)3to SnCl2or ZnCl2produces ClMo(N[t-Bu]Ar)3(71−93% for SnCl2) and RCN (97−99%). Magnesium metal reduces ClMo(N[t-Bu]Ar)3to Mo(N[t-Bu]Ar)3(74%), completing a synthetic cycle. New strategies for the functionalization of sterically hindered nitrides and nitrile extrusion from d2ketimides are presented in the context of a new route for derivatizing N2.