Stereoselective tandem 1,4-addition reactions for benzenes: a comparison of Os(II), Re(I), and W(0) systems.
Stereoselective tandem 1,4-addition reactions for benzenes: a comparison of Os(II), Re(I), and W(0) systems.
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苯的立体选择性串联 1,4-加成反应：Os(II)、Re(I) 和 W(0) 体系的比较。
DOI：
10.1021/ja047108p
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发表时间：
2004
期刊：
影响因子：
--
通讯作者：
Harman,WDean
中科院分区：
文献类型：
--
作者：
Ding,Fei;Harman,WDean
配合物TpRe（CO）（MeIm）（η 2-苯）（Tp =三（吡唑基）硼酸酯; MeIm = N-甲基咪唑）中的芳烃配体经历了串联的亲电/亲核1，4-加成反应。随后的氧化脱金属反应得到顺-3，6-二取代的1，4-环己二烯（46 − 84%）。将常见的有机亲电试剂如缩醛和迈克尔受体成功地加到结合的苯上，生成η 3-苯鎓配合物，然后将其与甲硅烷基烯酮缩醛、甲硅烷基乙烯基醚、苯基锂或丙二酸酯反应，得到1，4-二烷基化二氢苯配合物。d6过渡金属类似物TpW（NO）（PMe3）（η 2-苯）和[Os（NH3）5（η 2-苯）] 2+也发生1，4-二烷基化反应，并比较了所有三种金属活化芳烃的相对能力。
The arene ligand in the complex TpRe(CO)(MeIm)(η2-benzene) (Tp = hydridotris(pyrazolyl)borate; MeIm =N-methylimidazole) undergoes tandem electrophile/nucleophile 1,4-addition reactions. Subsequent oxidative demetalation affordscis-3,6-disubstituted 1,4-cyclohexadienes (46−84%). Common organic electrophiles such as acetals and Michael acceptors were successfully added to the bound benzene to generate η3-benzenium complexes, which then were treated with a silyl ketene acetal, silyl vinyl ether, phenyllithium, or malonate ester to afford 1,4-dialkylated dihydrobenzene complexes. The d6transition metal analogues TpW(NO)(PMe3)(η2-benzene) and [Os(NH3)5(η2-benzene)]2+also undergo 1,4-dialkylation reactions, and the relative ability of all three metals to activate arenes is compared.