源自丙二烯和亚氨基锆配合物的金属环的重排和立体突变。
Rearrangements and stereomutations of metallacycles derived from allenes and imidozirconium complexes.
作者信息
Michael Forrest E, Duncan Andrew P, Sweeney Zachary K, Bergman Robert G
机构信息
Department of Chemistry, University of California, Berkeley, CA 94720, USA.
出版信息
J Am Chem Soc. 2005 Feb 16;127(6):1752-64. doi: 10.1021/ja045607k.
Abstract
The mechanisms of the rearrangements and stereoinversion of azametallacyclobutenes generated via [2+2] cycloaddition of allenes and imidozirconium complexes have been studied. Metallacycles derived from allenes bearing beta-hydrogen atoms racemize at room temperature by reversible beta-hydride elimination, a process which is also responsible for their eventual conversion to monoazadiene complexes. Metallacycles derived from diarylallenes racemize by reversible thermal bond homolysis at 95 degrees C; racemization of these metallacycles is also catalyzed by mild oxidants.
摘要
通过丙二烯与亚氨基锆配合物的[2+2]环加成反应生成的氮杂金属环丁烯的重排和立体反转机制已得到研究。源自带有β-氢原子的丙二烯的金属环在室温下通过可逆的β-氢化物消除进行外消旋化，该过程也是它们最终转化为单氮二烯配合物的原因。源自二芳基丙二烯的金属环在95℃下通过可逆的热键均裂进行外消旋化；这些金属环的外消旋化也可由温和的氧化剂催化。
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