非对称的Ni-催化结合合合激活的恩
Joshua D Sieber1, James P Morken
1Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, USA.
Journal of the American Chemical Society
|March 15, 2008
概括
这项研究详细介绍了一种催化反应,用于使用基酸皮纳科尔的基基的酶选择性合. 实现了高的酶选择性,有利于复杂基质中的zylidene位点.
科学领域:
- 有机金属化学 有机金属化学
- 不对称的催化剂.
- 合成有机化学 合成有机化学
背景情况:
- 基基是多功能合成中间体.
- 异位选择性合是合成奇拉分子的关键.
- 为这些转变开发高效的催化系统仍然是一个挑战.
研究的目的:
- 开发一种新型催化酶的酸皮纳科尔 (allylB(pin)) 基利丁基的新型酶选择添加剂.
- 为了研究反应的机制和基质范围.
- 为了在结合过程中达到高的enantioselectivities.
主要方法:
- 催化反应采用酸纳醇. 催化反应使用酸纳醇.
- 使用非对称的dialkylidene ketones作为基质.
- 的14联体被用来诱导反选择性.
主要成果:
- 这种反应与各种基基具有很高的有效性.
- 在非对称基质中观察到青利丁位点对化的一种偏好.
- 获得了从91到94%eE的异能选择性,与性14获得.
- 拟议的机制涉及形成一个不和的pi-allyl复合体,然后进行减小性消除.
结论:
- 已经建立了一个高效的催化对dialkylidene ketones的enantioselective合并.
- 这种方法可以获得具有出色的enantiocontrol的奇拉产品.
- 反应机制为介导的催化循环提供了洞察力.
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