Isomers of (PhMeSi)6 and (PhMeSi)5

Isomers of (PhMeSi)6 and (PhMeSi)5
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(PhMeSi)6 和 (PhMeSi)5 的异构体

DOI:
10.1021/om00075a010
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发表时间:
1983
期刊:
影响因子:
2.8
通讯作者:
R. West
R. West
中科院分区:
化学2区
文献类型:
--
作者:
San;L. D. David;K. Haller;Cynthia L. Wadsworth;R. West

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结论中性CpMo(CO) 2 (α3-烯丙基)体系赋予与烯丙基片段相邻的亚甲基足够的氢特征,以允许氢化物提取。所得稳定的阳离子二烯体系不仅可以被软亲核试剂(例如烯胺)攻击,还可以被硬亲核试剂(例如格氏试剂)攻击。这与许多使用由极弱酸性试剂形成的亲核试剂进行还原分解的系统形成对比。我们预计这些系统将在天然产物或其合成前体的合成中具有重要价值。例如,他们可以为使用 Pearson 开发的 (二烯) Fe (CO) 3 的方法提供替代或补充方法,用于天然产物合成中的各种中间体。 18致谢。我们要感谢美国国家科学基金会对 NSF 东北地区 NMR 设施的支持(拨款 CHE-79-16210)。这项工作得到了国家科学基金会(Grant CHE-11201)的支持。
ConclusionsThe neutral CpMo (CO) 2 (?? 3-allyl) systems impart suf-ficient hydridic character to methylenes adjacent to the allyl fragment to allow hydride abstraction. The resulting stabilized cationic diene systems can be attacked, not only by soft nucleophiles such as enamines but also by hard nucleophiles such as Grignard reagents. This contrasts with many systems that undergo reductive decomposition with nucleophiles formed from very weakly acidic reagents. We anticipate that these systems will prove to be of significant value in the syntheses of natural products or their synthetic precursors. For example, they may provide alternative or complementary methodologies to those using (diene) Fe (CO) 3 developed by Pearson for a wide range of intermediates in natural product syntheses. 18Acknowledgment. We wish to thank the National Science Foundation for support of the NSF Northeast Regional NMR Facility (Grant CHE-79-16210). This work was supported by the National Science Foundation (Grant CHE-11201).