Reaction Diversity of the S–S Bond Promoted by Metal Coordination: From Discovery to Controllable Reactions
Reaction Diversity of the S–S Bond Promoted by Metal Coordination: From Discovery to Controllable Reactions
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DOI：
10.1002/ejic.200900913
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发表时间：
2010-03
影响因子：
2.3
通讯作者：
Hai‐Bin Zhu;Lei Li;Gang Xu;S. Gou
中科院分区：
文献类型：
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作者：
Hai‐Bin Zhu;Lei Li;Gang Xu;S. Gou
在甲醇/CH2Cl2混合溶剂中NiCl2配位的促进下，2-PPDS{bis[4-(pyridin-2-yl)pyrimidin-2-yl]disulfane}的二硫键发生了不同的原位S-S键反应，如S氧化、S-S键和C-S键断裂，生成了三个新的组分，鉴定为2-甲氧基-4-(吡啶-2-基)嘧啶。2-PPST{S-[4-(吡啶-2-基)嘧啶-2-基]4-(吡啶-2-基)嘧啶-2-磺代硫酸酯}和2-PPS{双[4-(吡啶-2-基)嘧啶-2-基]硫烷}。更重要的是，这样的原位反应可以得到有效的控制，从而以高度选择性的方式进行。因此，NiCl2介导的2-PPDs在反应混合物中连续鼓泡的原位反应只生成2-PPS，而用CuCl2(OAc)2取代NiCl2只生成2-MPP。验证性实验证明，2-ppst在这些原位反应中起着决定性的中间体作用。
Promoted by NiCl 2 coordination in the mixed solvent MeOH/ CH 2 Cl 2 , diverse in situ S-S bond reactions, such as S-oxidation and S-S and C-S bond scission, occurred in the disulfide ligand of 2-ppds {bis[4-(pyridin-2-yl)pyrimidin-2-yl]disulfane} to yield three new components identified as 2-mpp [2-methoxy-4-(pyridin-2-yl)pyrimidine], 2-ppst {S-[4-(pyridin-2-yl)pyrimidin-2-yl] 4-(pyridin-2-yl)pyrimidine-2-sulfonothioate} and 2-pps {bis[4-(pyridin-2-yl)pyrimidin-2-yl]sulfane}. More importantly, such in situ reactions could be efficaciously controlled so that they proceed in a highly selective manner. Thus, NiCl 2 -mediated in situ reaction of 2-ppds with the aid of continuous air bubbling through the reaction mixture exclusively led to 2-pps, whereas replacement of NiCl 2 by Cu(OAc) 2 afforded 2-mpp alone. A confirmatory experiment proved that 2-ppst served as a decisive intermediate in these in situ reactions.