Coupling of Fischer carbene complexes with conjugated enediynes featuring radical traps; Novel structure and reactivity features of chromium complexed arene diradical species.
Coupling of Fischer carbene complexes with conjugated enediynes featuring radical traps; Novel structure and reactivity features of chromium complexed arene diradical species.
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DOI：
10.1016/j.jorganchem.2008.08.003
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发表时间：
2008-10-15
影响因子：
2.3
通讯作者：
Herndon, James W.
中科院分区：
文献类型：
--
作者：
Zhang, Yi;Irshaidat, Tareq;Wang, Haixia;Waynant, Kris V.;Wang, Haobin;Herndon, James W.
研究了Fischer卡宾配合物与具有侧链烯基的共轭烯二炔的反应。反应通过卡宾-炔偶联进行以产生烯炔-烯酮中间体。该中间体然后经历摩尔环化以生成铬络合的芳烃双自由基，其然后经历与侧链烯烃基团的环化。自由基环化优选6-内模式，除非存在自由基稳定基团以有利于5-外模式。计算评估的单重态和三重态配置的中间双自由基物种。芳烃三重态双自由基的特点是在氧和离域铬的自旋密度最小。6-内环化产物在动力学和热力学上都是有利的。
The reaction of Fischer carbene complexes with conjugated enediynes that feature a pendant alkene group has been examined. The reaction proceeds through carbene-alkyne coupling to generate an enyne-ketene intermediate. This intermediate then undergoes Moore cyclization to generate a chromium complexed arene diradical, which then undergoes cyclization with the pendant alkene group. The radical cyclization prefers the 6-endo mode unless radical-stabilizing groups are present to favor the 5-exo mode. The intermediate diradical species were evaluated computationally in both the singlet and triplet configurations. Arene triplet diradicals feature minimal spin density at oxygen and delocalization to chromium. The 6-endo cyclization product was kinetically and thermodynamically favored.
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影响因子：
3.6
作者：
GAYO, LM;WINTERS, MP;MOORE, HW
通讯作者：
MOORE, HW
影响因子：
4.4
作者：
DOLG, M;WEDIG, U;PREUSS, H
通讯作者：
PREUSS, H
影响因子：
4.4
作者：
BECKE, AD
通讯作者：
BECKE, AD
影响因子：
4.9
作者：
Manner, Virginia W.;Markle, Todd F.;Mayer, James M.
通讯作者：
Mayer, James M.
DOI：
10.1007/bf01114537
发表时间：
1990-04-01
期刊：
THEORETICA CHIMICA ACTA
影响因子：
--
作者：
ANDRAE, D;HAUSSERMANN, U;PREUSS, H
通讯作者：
PREUSS, H