Asymmetric Binary-Acid Catalysis with InBr3 in the Inverse-Electron-Demanding Hetero-Diels-Alder Reaction of Mono- and Bis-Substituted Cyclopentadienes: Remote Fluoro-Effect on Stereocontrol
作者:Jian Lv、Long Zhang、Shenshen Hu、Jin-Pei Cheng、Sanzhong Luo
DOI:10.1002/chem.201103340
日期:2012.1.16
Remote F effect: Unprecedented hetero‐Diels–Alder reactions of mono‐ and bis‐substituted cyclopentadienes have been realized by an asymmetric binary‐acid catalyst that synergistically combines a chiral phosphoric acid 1 h/InBr3 with good periselectivity, high regioselectivity, and excellent stereoselectivity. Substituent mapping of the chiral phosphoric acid indicates a dramatic remote ortho‐fluoro
遥远的F效应:单和双取代的环戊二烯的前所未有的杂狄尔斯-阿尔德反应已通过不对称的二元酸催化剂实现,该催化剂将手性磷酸1 h / InBr 3协同结合,具有良好的选择性,高区域选择性和优异的选择性立体选择性。手性磷酸的取代基作图表明对立体控制有显着的远距离邻氟影响(参见方案)。
Synthesis and properties of sterically congested cyclopentadienes and their transition metal complexes
作者:T.Jeffrey Clark、Christopher M. Killian、Sanjay Luthra、Terence A. Nile
DOI:10.1016/0022-328x(93)83365-3
日期:1993.12
The synthesis of 1,3-dialkyl substituted cyclopentadienes, C5H4RR′, Cp′H (Va–g) (where R and R′ are tert-butyl, iso-propyl, neo-pentyl, cyclohexyl, or 1-methylcyclohexyl) is reported. These are synthesized by the nucleophilic addition of methyl or hydride anions to the corresponding 2-alkyl-6,6-dialkylfulvenes (IIIa–f) followed by hydrolysis. These substituted 1,3-cyclopentadienes have been converted
1,3-二烷基取代的环戊二烯,C 5 H 4 RR',CP'H(Va–g)(其中R和R'为叔丁基,异丙基,新戊基,环己基或1-甲基环己基)。这些是通过将甲基或氢化物阴离子亲核加成到相应的2-烷基-6,6-二烷基富勒烯(IIIa–f)中,然后水解而合成的。这些取代的1,3-环戊二烯已转化为有机金属衍生物例如[CP'Fe(CO)2 ] 2,[CP'M(CO)3本人](MMo或W)和CP' 22Fe。为了研究取代的环戊二烯基配体的空间和电子性质,已经研究了所选配合物的光谱和电化学性质。