State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences , Shanghai 200032, China.
Collaborative Innovation Center of Chemical Science and Engineering , Tianjin 300072, China.
J Am Chem Soc. 2015 Nov 25;137(46):14594-7. doi: 10.1021/jacs.5b10310. Epub 2015 Nov 11.
The first catalytic enantioselective ring-opening reaction of donor-acceptor cyclopropanes with water is described. By employing Cy-TOX/Cu(II) as catalyst, the reaction performed very well over a broad range of substrates, leading to the ring-opening products in 70-96% yields with up to 95% ee under mild conditions. The current method provides a new approach to direct access to γ-substituted GBH derivatives very efficiently. Importantly, Cu(ClO4)2·6H2O proves to serve as both a Lewis acid and a source of water, which affords a fine system to controllably release water as a nucleophile in the asymmetric catalysis.
首次描述了给体-受体环丙烷与水的催化对映选择性开环反应。通过使用 Cy-TOX/Cu(II) 作为催化剂，该反应在广泛的底物范围内表现非常出色，在温和条件下以高达 95%的对映选择性得到 70-96%的开环产物。目前的方法为高效地直接获得 γ-取代 GBH 衍生物提供了一种新途径。重要的是，Cu(ClO4)2·6H2O 被证明既可以作为路易斯酸，也可以作为水的来源，这为在不对称催化中可控地释放水作为亲核试剂提供了一个优良的体系。
