通过高旋转 ((II) 复合物的Z-选择性烯异构化
Chi Chen1, Thomas R Dugan, William W Brennessel
1Department of Chemistry, University of Rochester , 120 Trustee Road, Rochester, New York 14627, United States.
Journal of the American Chemical Society
|January 7, 2014
概括
研究人员开发了 (II) 催化剂,可选择性异构化简单的基到不太稳定的Z-异构体. 这一突破为控制烯合成中的立体化学提供了一种新的方法.
科学领域:
- 有机金属化学 有机金属化学
- 催化剂是一种催化剂.
- 立体选择性合成 立体选择性合成
背景情况:
- 烯异构化通常有利于更稳定的E-异构体.
- 由于热力学偏好,Z-烯的选择性合成具有挑战性.
研究的目的:
- 通过异构化开发一种用于选择性Z-烯形成的催化系统.
- 为了阐明催化异构的机制.
主要方法:
- 使用的 ((II) 催化剂具有重的β-二甲基酸连接体.
- 采用同位素标记实验来研究反应中间体.
- 开发了一个硬质模型来解释立体选择性.
主要成果:
- 实现了1-烯的选择性异构化到Z-2-烯.
- 确定了一个三坐标的 ((II) 复合物作为静止状态.
- 证明了各种基质的催化剂有效性,包括西兰和以太.
结论:
- (II) 催化剂与重的配体使Z-合成的动力控制成为可能.
- 该机制涉及快速的β-化物消除和[1,2]-插入步骤.
- 过渡状态中的立体因素决定了Z-立体选择性.
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