Concerning the potential reversibility of carbometalation in alkoxide-directed Ti(Oi-Pr)4-mediated reductive cross-coupling of homoallylic alcohols with aromatic imines.

Concerning the potential reversibility of carbometalation in alkoxide-directed Ti(Oi-Pr)4-mediated reductive cross-coupling of homoallylic alcohols with aromatic imines.
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关于醇盐引导的 Ti(Oi-Pr)4 介导的高烯丙醇与芳香亚胺的还原交叉偶联中碳金属化的潜在可逆性。

DOI:
10.1039/b927430h
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发表时间:
2010
期刊:
Chemical communications (Cambridge, England)
影响因子:
--
通讯作者:
Micalizio,GlennC
Micalizio,GlennC
中科院分区:
--
文献类型:
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作者:
Takahashi,Masayuki;Micalizio,GlennC

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为了了解ti介导的同丙烯醇和亚胺之间的还原交叉偶联的选择性性质,我们研究了假设的有机金属中间体的热力学平衡是否在选择性中起作用。在预成形的氮杂环戊烷中没有发现烯烃交换的证据,这一观察结果与基于动力学控制的选择性碳金属化的模型一致。
In an attempt to understand the nature of selectivity in Ti-mediated reductive cross-coupling between homoallylic alcohols and imines, we investigated whether thermodynamic equilibration of the presumed organometallic intermediate plays a role in selectivity. No evidence could be found for olefin exchange in preformed azatitanacyclopentanes—an observation that is consistent with a model based on kinetically controlled selective carbometalation.