A new generation of π-basic dearomatization agents

被引:131
作者
Keane, JM
Harman, WD
机构
[1] Univ Virginia, Dept Chem, Charlottesville, VA 22904 USA
[2] Muhlenberg Coll, Dept Chem, Allentown, PA 18104 USA
关键词
D O I
10.1021/om050029h
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
A new generation of dearomatizing pi-bases having the general form {TpM(L)(pi-acid)} (where Tp = hydridotris(pyrazolyl)borate, M = rhenium, molybdenum, tungsten, L = variable ligand, and pi-acid = CO, NO+) has been developed. These fragments show reactivity patterns similar to those of their pentaammineosmium(II) predecessor, binding aromatic molecules across two carbons and subsequently activating these ligands toward electrophilic addition and cycloaddition reactions. In many cases, these second-generation dearomatization agents show a greater degree of pi-back-bonding than was observed for the analogous pentaammineosmium(II) complexes. A number of unprecedented reaction pathways have been discovered for these second-generation systems, most notably a broad array of cyclization reactions. In addition, these chiral-at-metal dearomatization agents are readily resolved and have been utilized in reaction sequences to give highly enantioenriched polycyclic molecules from common aromatic precursors.
引用
收藏
页码:1786 / 1798
页数:13
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