Ligand-modulated stereo- and regioselective tandem addition reactions of rhenium-bound naphthalene.
Ligand-modulated stereo- and regioselective tandem addition reactions of rhenium-bound naphthalene.
复制标题
配体调节的铼结合萘的立体和区域选择性串联加成反应。
DOI：
10.1021/ja012066f
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发表时间：
2002
影响因子：
15
通讯作者：
Harman,WDean
中科院分区：
文献类型：
--
作者：
Valahovic,MarkT;Gunnoe,TBrent;Sabat,Michal;Harman,WDean
一系列形式为TprE(CO)(L)(η2-萘)(TP=氢化(吡唑基)硼酸酯)的配合物进行了串联的亲电/亲核加成反应，其区域可控程度取决于辅助配体L。当L=PMe3时，η2-萘络合物与三苯甲酸的反应有利于1，4-加成产物的生成，而当L=吡啶、N，N-二甲氨基吡啶、N-甲基咪唑或NH31时，有利于1，2-加成产物的生成。这些反应在良好的立体控制下进行： 亲水性(H+，D+)和亲核性(硅基酮缩醛)都在金属配位的表面添加了反，并且每个反应都可以分离出一个配位非对映异构体。稀土络合物的单电子氧化以较高的产率得到相应的游离二氢萘。
A series of complexes of the form TpRe(CO)(L)(η2-naphthalene) (Tp = hydridotris(pyrazolyl)borate) undergoes tandem electrophile/nucleophile addition reactions with a high degree of regiocontrol depending on the auxiliary ligand, L. When L = PMe3, the reaction of the η2-naphthalene complex with triflic acid followed by a silyl ketene acetal favors the 1,4-addition product, whereas when L = pyridine,N,N-dimethylaminopyridine,N-methylimidazole, or NH3the 1,2-addition product is favored. These reactions proceed with excellent stereocontrol: both electrophile (H+, D+) and nucleophile (silyl ketene acetal) add anti to the face of metal coordination, and a single coordination diastereomer can be isolated for each reaction. One-electron oxidation of the Re complex affords the corresponding free dihydronaphthalene in good yield.