螺环单磷配体在α-烷基取代烯酰胺不对称催化氢化中的应用-有机化学专业毕业论文.docxVIP

PAGE PAGE iv Abstract Chiral amine is an essential structural unit in natural products and a key function group in many biologically active molecules. Rhodium-catalyzed asymmetric hydrogenation of enamides is one of the most efficient methods to produce chiral primary and secondary amine derivatives. Althought significant progresses have been achieved in transition metal-catalyzed highly enantioselective hydrogenation of ?-aryl enamines in the past decades, few attention has been paid on asymmetric hydrogenation of ?-alkyl enamides. In this dissertation, we accomplished the rhodium-catalyzed asymmetric hydrogenation of ?-alkyl enamines using monodentate phosphorus ligands containing 1,1-spirobiindane backbone. The monodentate spiro phosphonite ligands was successfully applies in rhodium -catalyzed asymmetric hydrogenation of (Z)-N-(1-phenylprop-1-en-2-yl)acetamide derivatives. Under the optimal reaction conditions the corresponding reducting product, tertiary amines were obtained in high yields with excellent enantioselectivities (up to 95% ee). Furthermore, rhodium-catalyzed asymmetric hydrogenation of (E)-N-(1-phenylprop-1-en-2-yl)acetamide derivatives was also investigated with monodentate spiro phospholane ligands, and the excellent enantioselectivities (up to 97% ee) have been achieved for a wide rang of substrate scopes. This is the first highly enantioselective hydrogenation of E-(?-alkyl)enamides. These work represents the first rhodium/monodentate phosphorus catalyzed highly enantioselective hydrogenation of ?-alkyl substituted enamides and provided an effective method to prepare chiral ?-aryliospropylamine derivatives. Eleven new compounds were synthesized in this thesis. Their structures were identified by 1H NMR, 13C NMR, HRMS or elemental analysis. Keywords: enamides, spiro monodentate phosphorus, rhodium, catalytiac asymmetric hydrogenation. 目 录 第一章 前言 1 1.1 不对称催化氢化 3 1.2 烯酰胺的不对称催化氢化反应 4 1.3 立题思想 8 参考文献 11 第二章 铑/螺环单磷配体配合物催化?-烷基取代烯酰胺的不对称氢 化反应研究