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Magnesiacyclopentadienes as Alkaline‐Earth Metallacyclopentadienes: Facile Synthesis, Structural Characterization, and Synthetic Application
Author(s) -
Wei Junnian,
Liu Liang,
Zhan Ming,
Xu Ling,
Zhang WenXiong,
Xi Zhenfeng
Publication year - 2014
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201310116
Subject(s) - reagent , chemistry , alkaline earth metal , characterization (materials science) , metal , combinatorial chemistry , inorganic chemistry , nanotechnology , materials science , organic chemistry
Metallacyclopentadienes have attracted much attention as building blocks for synthetic chemistry as well as key intermediates in many metal‐mediated or metal‐catalyzed reactions. However, metallacyclopentadienes of the alkaline‐earth metals have not been reported, to say nothing of their structures, reaction chemistry, and synthetic applications. In this work, the first series of magnesiacyclopentadienes, spiro‐dilithio magnesiacyclopentadienes, and dimagnesiabutadiene were synthesized from 1,4‐dilithio 1,3‐butadienes. Single‐crystal X‐ray structural analysis of these magnesiacycles revealed unique structural characteristics and bonding modes. Their reaction chemistry and synthetic application were preliminarily studied and efficient access to amino cyclopentadienes was established through their reaction with thioformamides. Experimental and DFT calculations demonstrated that these magnesiacyclopentadienes could be regarded as bis(Grignard) reagents wherein the two MgC(sp 2 ) bonds have a synergetic effect when reacting with substrates.