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高能量立体手性钌卡宾的合成、分离、结构鉴定和反应性：通过烯烃复分解和其他途径的立体化学反转。

Synthesis, isolation, characterization, and reactivity of high-energy stereogenic-at-Ru carbenes: stereochemical inversion through olefin metathesis and other pathways.

机构信息

Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, United States.

出版信息

J Am Chem Soc. 2012 Aug 1;134(30):12438-41. doi: 10.1021/ja3056722. Epub 2012 Jul 20.

DOI:10.1021/ja3056722
PMID:22816554
Abstract

The synthesis, isolation, purification (routine silica gel chromatography), and spectroscopic characterization of high-energy endo stereogenic-at-Ru complex isomers, generated by ring-opening/cross-metathesis (ROCM) reaction of the corresponding exo carbenes, are disclosed. We provide experimental evidence showing that an endo isomer can undergo thermal or Brønsted acid-catalyzed polytopal rearrangement, causing conversion to the energetically favored exo carbene.

摘要

本文公开了通过相应的外消旋卡宾的开环/交叉复分解（ROCM）反应生成的高能内消旋立体中心- Ru 配合物异构体的合成、分离、纯化（常规硅胶色谱法）和光谱特性。我们提供了实验证据，表明内消旋异构体可以经历热或布朗斯台德酸催化的多面体重排，导致转化为能量上有利的外消旋卡宾。

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