3846-66-0Relevant articles and documents
Catalytic C=N bond formation by metal-imide-mediated imine metathesis
Cantrell, Gidget K.,Meyer, Tara Y.
, p. 8035 - 8042 (1998)
Molybdenum bis(imide) complexes of the general formula (DME)Cl2Mo(=NR)2 catalytically metathesize acyclic imine substrates. This C=N bond-forming reaction has significant implications for the synthesis of small molecules by ring-closing metathesis and polymers by ring-opening metathesis. A series of closely related =NR transfer reactions were examined in an effort to fully understand the process. (RO)2Mo(=CHR')(=NAr) (1a, Ar = 2,6-diisopropylphenyl in all cases; R = C(CF3)2CH3) underwent alkylidene/imine exchange with a variety of imines in situ to give a mixed bis(imide) product and an olefin. The reactivity decreased if the alkoxide substituents were changed for more electron donating ones. (DME)Cl2Mo(=NR)2 (3a, R = 2,6-diisopropylphenyl; 4, R = t-Bu) reacted with imines in an imide/imine metathesis to give mixed bis(imide) complexes and new imines. The reaction rates depended strongly on the steric demands of the imide NR substituent. Replacement of the chlorides with more electron donating alkoxide ligands inhibited the reactions. Compounds 3a and 4 also exchanged imide ligands with each other (imide/imide metathesis). Finally, compounds 3a and 4 were found to catalytically metathesize mixtures of two imines at 80 °C in 105 and 22 h, respectively. It was established that the reaction is mediated by the presence of unique initiation products in catalytic mixtures. A catalytic cycle is proposed and the nature of the mechanism is discussed in terms of the data gathered on all of the metatheses.
Reductive Difunctionalization of Aryl Alkenes with Sodium Metal and Reduction-Resistant Alkoxy-Substituted Electrophiles
Fukazawa, Mizuki,Nogi, Keisuke,Sasamori, Takahiro,Takahashi, Fumiya,Yorimitsu, Hideki
supporting information, (2020/03/13)
A general method for alkali-metal-promoted reductive difunctionalization of alkenes has been developed by means of reduction-resistant alkoxy-substituted electrophiles. A series of 1,2-diboration and 1,2-dicarbofunctionalization products can be synthesize
Stereo-controlledanti-hydromagnesiation of aryl alkynes by magnesium hydrides
Chiba, Shunsuke,Li, Yihang,Ong, Derek Yiren,Pang, Jia Hao,Takita, Ryo,Wang, Bin,Watanabe, Kohei
, p. 5267 - 5272 (2020/06/04)
A concise protocol foranti-hydromagnesiation of aryl alkynes was established using 1?:?1 molar combination of sodium hydride (NaH) and magnesium iodide (MgI2) without the aid of any transition metal catalysts. The resulting alkenylmagnesium intermediates could be trapped with a series of electrophiles, thus providing facile accesses to stereochemically well-defined functionalized alkenes. Mechanistic studies by experimental and theoretical approaches imply that polar hydride addition from magnesium hydride (MgH2) is responsible for the process.