Chiral Ru-based complexes for asymmetric olefin metathesis: Enhancement of catalyst activity through steric and electronic modifications
Chiral Ru-based complexes for asymmetric olefin metathesis: Enhancement of catalyst activity through steric and electronic modifications
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DOI：
10.1021/ja0302228
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发表时间：
2003-10-15
影响因子：
15
通讯作者：
Hoveyda, AH
中科院分区：
文献类型：
--
作者：
Van Veldhuizen, JJ;Gillingham, DG;Hoveyda, AH
公开了六种对映体纯的Ru基复分解催化剂的设计、合成、表征和催化活性（3a-3f）。通过对母体催化剂体系的空间位阻和电子结构的改变，制备了新的手性催化剂（3）。目前的研究表明，手性配合物3的结构修饰效果并不总是与相关非手性配合物的效果相对应。目前的研究结果表明，改性的钌配合物（3e和3f）提供的反应性水平是超过2个数量级高于3。提供的反应性和物理数据阐明了活性差异的起源。新一代手性Ru催化剂的一些成员促进不对称开环（AROM）和闭环（ARCM）复分解，这不能由第一代手性催化剂（3）实现。
Design, synthesis, characterization, and catalytic activity of six enantiomerically pure Ru-based metathesis catalysts are disclosed (3a-3f). The new chiral catalysts were prepared through steric and electronic alterations of the parent catalyst system (3). The present studies indicate that the effect of structural modifications of chiral complex 3 does not always correspond to those of the related achiral complexes. The present findings illustrate that modified Ru complexes (3e and 3f) deliver reactivity levels that are more than 2 orders of magnitude higher than 3. Reactivity and physical data are provided that shed light on the origin of activity differences. Some members of the new generation of chiral Ru catalysts promote asymmetric ring-opening (AROM) and ring-closing (ARCM) metatheses that cannot be effected by the first generation chiral catalyst (3).