上海有机所合成讲义第11讲.pptVIP

Sorensen and coworkers recently reported the synthesis of (–)-hispidospermidin (Sorensen JACS.2000, 122, 9556). The Shapiro Reaction, along with methodology developed by Whitesell, was use in the construction of intermediate 3 from the indicated building blocks 1 and 2 (eq 1). Provide a mechanism for: the Shapiro Reaction of 1 to intermediate B; the transformation of intermediate B to the illustrated product 3 and use 3-dimensional representations to illustrate the stereochemical aspects of this individual step. 第十二节 烯烃的制备 P, As, Sb, Bi, S, Se, Te, B, Si, Sn, Pb etc. § 2-12-1 叶立德的制备 § 2-12-2 叶立德的制备 Salt Deprotonation Carbene and/or Carbenoid Transformation Nucleophilic Addition Hou et al. J. Org. Chem. 2004, in press. § 2-12-3 膦叶立德 Regioselectivity Stereoselectivity Stabilized ylide: E-isomer favored Semi-stabilized ylide: poor selectivity Non-stabilized ylide: Z-isomer favored 立体化学及其控制 Stabilized ylide: E-isomer favored 机理 Anorg. Chem. Org. Chem. 1980, 1455. please see: J. Am. Chem. Soc. 1963, 85, 3878. Semi-stabilized ylide: poor selectivity Controllable Synthesis of E and Z Olefin 机理 Non-stabilized ylide: cis favored 极性溶剂： 降低温度： 锂盐存在： Cis ? Cis ? Cis ? OH, NH2 无需保护 Synthesis of E-isomer Shanghai, China § 7-3 Hydrazone-based Transformations Wolff-Kischner Reduction Wharton Rearrangement Eschenmoser-Tanabe Fragmentation Reduction of Tosyl Hydrazones: The Alkene Walk“ Tosyl Hydrazone-Based Fragment Coupling The Shapiro Reaction Bamford-Stevens Reaction Wolff-Kischner Reduction PPh3 首先进攻DEAD The Shapiro Reaction Shanghai, China * * * *