Yue Wen-Jun, Zhang Cheng-Yuan, Yin Liang
CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Centre for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China.
CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Centre for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China.
iScience. 2019 Apr 26;14:88-99. doi: 10.1016/j.isci.2019.03.010. Epub 2019 Mar 16.
Two catalytic asymmetric vinylogous aldol-type reactions of aldehydes with allyl phosphonate and allyl sulfone have been uncovered in good to high yields for the first time. The bulky ligand-(R)-DTBM-SEGPHOS-was found to be the key to perfectly control both regio- and enantioselectivities. Transformations of the vinylogous products (including Horner-Wadsworth-Emmons and Julia olefinations) were successfully realized by virtue of the phosphonate and sulfone moieties. Moreover, the present methodology was successfully applied in the asymmetric synthesis of natural products.
首次发现了醛与烯丙基膦酸酯和烯丙基砜的两种催化不对称乙烯基类似物醛醇型反应，产率良好至高。发现庞大的配体-（R）-DTBM-SEGPHOS-是完美控制区域和对映选择性的关键。借助膦酸酯和砜部分，成功实现了乙烯基类似物产物的转化（包括霍纳-沃兹沃思-埃蒙斯反应和朱莉娅烯烃化反应）。此外，本方法成功应用于天然产物的不对称合成。
