通过六个组成的Palladacycles激活C ((alkenyl) -H:催化1,3-合成
Mingyu Liu1, Pusu Yang1, Malkanthi K Karunananda1
1Department of Chemistry , The Scripps Research Institute , 10550 North Torrey Pines Road , La Jolla , California 92037 , United States.
Journal of the American Chemical Society
|April 10, 2018
概括
这项研究引入了一种新的催化方法,通过催化C-H激活从两个中合成高度置换的1,3-二烯. 这种多功能方法适用于各种基质,包括具有挑战性的内部基.
科学领域:
- 有机化学
- 催化剂
- 合成方法
背景情况:
- 1,3-二烯是有机合成中的关键组成部分.
- 以往合成替代的1,3-二烯的方法在基质范围和效率上往往面临限制.
- 内部非结合是C-H激活策略的特别具有挑战性的基质.
研究的目的:
- 开发一种用于合成高度替代的1,3-的新型催化方法.
- 使用有针对性的,介导的C-H激活策略.
- 扩大1,3-二烯合成的基质范围,包括具有挑战性的内部基.
主要方法:
- 采用了2催化C2H激活策略.
- 使用了三种含有双酸辅助物质的基质类别:4-酸,醇和双胺.
- 使用二氧化 (MnO2) 或 (II) 乙酸 (Co) 和氧 (O2) 的组合实现了催化周转.
主要成果:
- 该方法成功地从两个不同的中制备了高度替代的1,3-二烯.
- 这种转换在测试的基质类别中显示出广泛的范围.
- 内部非结合,以前是难以承受的基质.
- 实验和计算研究阐明了反应机制和选择性.
- 一种独特的二聚中间体被分离和特征化.
结论:
- 已经建立了一种通用和高效的催化方法来合成高度替代的1,3-二烯.
- 开发的C ((alkenyl) -H激活策略克服了以前的方法的局限性,特别是内部.
- 这项研究提供了对催化二烯合成的机理见解.
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