钴催化的四取代不饱和羧酸的不对称氢化与新型双膦配体的合成与应用

  手性羧酸是一类重要的化合物，广泛存在于医药、天然产品和农用化学品中。 过渡金属催化不饱和羧酸的不对称氢化是合成此类化合物的最有 效方法之一。科学家对各类过渡金属， 如 Ru、Rh、 Ir，甚至是廉价过渡金 属，如 Co 等催化二取代和三取代不饱和羧酸的不对称氢化进行了深入的研 究， 但是对于具有挑战性的四取代 α,β- 不饱和羧酸的不对称催化氢化研究 还未探索详尽，而有关于廉价金属 Co 催化的四取代不饱和羧酸不对称氢化 的研究也是首次。 我们通过大量的实验发展了一类钴( II)/Ph-BPE 催化环 和无环四取代不饱和羧酸的不对称氢化体系。 该催化体系具有较广的底物 适应性， 并且产物手性羧酸的产率高， 对映体选择性优异 （ 产率最高可达 98%， ee 值最高可达 99% ）。 具有潜在的替代贵金属催化剂的工业化价值 与能力。

  在不对称氢化发展史中， 手性配体是不对称氢化的重要组成部分，而 手性双膦配体在手性配体里面占据着极其重要的地位。 从最早的 DIOP 到Binaphane、 f-Binaphane 等， 双膦配体自从被化学家们开发出来后发展迅 速。 XantPhos 是 一 类 具 有 多 种 反 应 催 化 活 性 的 优 良 手 性 配 体 ， 我 们 在 Binaphane、 f-Binaphane 以及 XantPhos 的基础上，自主设计并合成了具 有三种配体优势合一体的新型手性配体 X-Binaphane， 该配体同时具备富 电子与大螯合角的天然优势， 在催化亚胺不对称氢化方面具有天然的骨架 优势，并且我们还成功地利用 Ir 配合 X- Binaphane 催化了二氢罂粟碱盐酸 盐的不对称氢化，取得了高达 99%的产率与 98%的 ee 值。

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