铜 (I) 催化对酸的选择性添加
Xiao-Feng Wei1, Xiao-Wei Xie1, Yohei Shimizu1
1Graduate School of Pharmaceutical Sciences, The University of Tokyo , Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Journal of the American Chemical Society
|March 21, 2017
概括
一种新的铜催化方法使得可以对基进行反选择性添加. 这产生了具有高选择性和功能组耐受性的有价值的性三级酒精.
科学领域:
- 有机化学
- 催化剂
- 不对称的合成
背景情况:
- 三级酒精是有机合成的重要组成部分.
- 开发对它们的合成具有选择性的方法是非常可取的.
- 跳过的酶具有作为稳定的前核友的潜力,但需要特定的激活策略.
研究的目的:
- 开发一种新型的铜催化酶选择性添加被跳过的氨酸到氨酸.
- 用跳过的基因作为稳定的碳化合物前核素来构建性三级酒精.
- 在加法反应中实现高水平的立体控制和化学选择性.
主要方法:
- 采用一个合铜 (I) 的布伦斯特德基催化剂与一种性二素联体, (S,S) -Ph-BPE.
- 使用化学选择性脱质化跳过的基因,而不是更酸的基因α-质子.
- 鉴定基丰富的三级酒精产品和分析反应立体化学.
主要成果:
- 一系列子中成功添加被跳过的酶.
- 由此产生的三级酒精具有高反体丰富性和二选择性.
- 显示出优异的基质通用性和功能组耐受性.
- 单独将被跳过的enyne部分转换为cis-conjugated enynes,使进一步的转换成为可能.
结论:
- 已经建立了一种简单而有效的方法,用于从跳过的和中合成聚丰富的三级醇.
- 开发的催化系统具有显著的选择性,克服了与基质酸度相关的挑战.
- 由此产生的cis-conjugated enynes作为后续合成操作的多功能中间体.
相关概念视频
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