Elusive Terminal Copper Arylnitrene Intermediates
Elusive Terminal Copper Arylnitrene Intermediates
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DOI：
10.1002/anie.201611275
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发表时间：
2017-06-01
影响因子：
16.6
通讯作者：
Warren, Timothy H.
中科院分区：
文献类型：
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作者：
Bakhoda, Abolghasem (Gus);Jiang, Quan;Warren, Timothy H.
在这里，我们报道了芳氮化物N3Ar与大体积铜(I)β-二酮酸酯之间的三种新的反应模式。将N3ArX3(Ar-X3=2，4，6-X3C6H2；X=Cl或Me)加到[(Pr2NN)-Pr-i]Cu(NCMe)中，得到叠氮对β-二酮亚胺主链的三氮杂环化合物。[(Pr2NN)-Pr-I]Cu(NCMe)与体积较大的叠氮化物N3Ar反应生成末端硝烯[(Pr2NN)-Pr-I][(Pr2NN)-Pr-I]=NaR，通过在芳基硝烯p位形成C-C键进行二聚得到双铜(II)二酮亚胺4(Ar=2，6-(Pr2C6H3)-Pr-I)或经腈插入得到重氮杂环丁烯8(Ar=4-Ph-2，6-IPR(2)C(6)H(2))。重要的是，反应性研究揭示了4和8都是末端硝烯[(Pr2NN)-Pr-I]Cu=NAR的“掩蔽”形式，它们经历了硝基转移到PMe3，(BuNC)-Bu-t，甚至转移到乙苯的苄基sp(3)C-H键。
We report herein three new modes of reactivity between arylazides N3Ar with a bulky copper(I) beta-diketiminate. Addition of N3ArX3 (Ar-X3 = 2,4,6-X3C6H2; X = Cl or Me) to [(Pr2NN)-Pr-i]Cu(NCMe) results in triazenido complexes from azide attack on the beta-diketiminato backbone. Reaction of [(Pr2NN)-Pr-i] Cu(NCMe) with bulkier azides N3Ar leads to terminal nitrenes [(Pr2NN)-Pr-i] Cu]=NAr that dimerize via formation of a C-C bond at the arylnitrene p-position to give the dicopper( II) diketimide 4 (Ar=2,6-(Pr2C6H3)-Pr-i) or undergo nitrile insertion to give diazametallocyclobutene 8 (Ar=4-Ph-2,6-iPr(2)C(6)H(2)). Importantly, reactivity studies reveal both 4 and 8 to be "masked" forms of the terminal nitrenes [(Pr2NN)-Pr-i]Cu=NAr that undergo nitrene group transfer to PMe3, (BuNC)-Bu-t, and even into a benzylic sp(3) C-H bond of ethylbenzene.