Diverse Reactivity of an Electrophilic Phosphasilene towards Anionic Nucleophiles: Substitution or Metal-Amino Exchange.
Diverse Reactivity of an Electrophilic Phosphasilene towards Anionic Nucleophiles: Substitution or Metal-Amino Exchange.
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DOI：
10.1002/anie.201605699
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发表时间：
2016-08
影响因子：
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通讯作者：
Philipp Willmes;Lukas Junk;V. Huch;C. B. Yildiz;D. Scheschkewitz
中科院分区：
文献类型：
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作者：
Philipp Willmes;Lukas Junk;V. Huch;C. B. Yildiz;D. Scheschkewitz
MesLi (Mes=2,4,6-三甲基苯基)与亲电磷硅烯 R2 (NMe2 )Si-RSi=PNMe2 (2, R=Tip=2,4,6-三异丙基苯基)的反应干净地提供了 R2 (NMe2 )Si-RSi=PMes，从而提供了在未受干扰的 Si=P 键处发生取代反应的第一个例子。在甲苯中，2 与二硅化锂的反应 R2 Si=Si(R)Li (1) 显然也通过初始亲核取代步骤进行（如 DFT 计算所示），但提供了饱和双环[1.1.0]丁烷类似物作为最终产物，其进一步被表征为其 Fe(CO)4 络合物。相比之下，在 1,2-二甲氧基乙烷中，1 与 2 的反应导致前所未有的金属-氨基交换反应。
The reaction of MesLi (Mes=2,4,6-trimethylphenyl) with the electrophilic phosphasilene R2 (NMe2 )Si-RSi=PNMe2 (2, R=Tip=2,4,6-triisopropylphenyl) cleanly affords R2 (NMe2 )Si-RSi=PMes and thus provides the first example of a substitution reaction at an unperturbed Si=P bond. In toluene, the reaction of 2 with lithium disilenide, R2 Si=Si(R)Li (1), apparently proceeds via an initial nucleophilic substitution step as well (as suggested by DFT calculations), but affords a saturated bicyclo[1.1.0]butane analogue as the final product, which was further characterized as its Fe(CO)4 complex. In contrast, in 1,2-dimethoxyethane the reaction of 1 with 2 results in an unprecedented metal-amino exchange reaction.