Institut für Organische Chemie und Biochemie, Albert-Ludwigs-Universität, Alberstr. 21, 79104, Freiburg, Germany.
Angew Chem Int Ed Engl. 2017 Feb 1;56(6):1520-1524. doi: 10.1002/anie.201610876. Epub 2017 Jan 12.
The rhodium-catalyzed atom-economic asymmetric N-selective intermolecular addition of purine derivatives to terminal allenes is reported. Branched allylic purines were obtained in high yields, regioselectivity and outstanding enantioselectivity utilizing a Rh/Josiphos catalyst. Conversely, linear selective allylation of purines could be realized in good to excellent regio- and E/Z-selectivity with a Pd/dppf catalyst system. Furthermore, the new methodology was applied to a straightforward asymmetric synthesis of carbocyclic nucleoside abacavir.
报道了铑催化的原子经济性不对称 N-选择性嘌呤衍生物与末端丙二烯的分子间加成反应。利用 Rh/Josiphos 催化剂，可以高收率、区域选择性和优异的对映选择性得到支链烯丙基嘌呤。相反，Pd/dppf 催化剂体系可以实现嘌呤的线性选择性烯丙基化，区域和 E/Z 选择性良好到优异。此外，该新方法学还应用于碳环核苷阿巴卡韦的直接不对称合成。
