5659-93-8Relevant articles and documents
A Convenient Synthesis of a Macrocyclic Dioxo Pentaamine and X-ray Crystal Structure of Its Monohydrazoic Acid Salt
Kimura, Eiichi,Anan, Hideki,Koike, Tohru,Shiro, Motoo
, p. 3998 - 4000 (1989)
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Gortler,L.B.,Saltzman,M.D.
, p. 3821 - 3823 (1966)
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Nickel-Catalyzed Asymmetric Hydroarylation of Vinylarenes: Direct Enantioselective Synthesis of Chiral 1,1-Diarylethanes
Tran, Hai N.,Burgett, Russell W.,Stanley, Levi M.
, p. 3836 - 3849 (2021/03/01)
The enantioselective hydroarylation of vinylarenes catalyzed by a chiral, non-racemic nickel catalyst is presented as a facile method to generate chiral 1,1-diarylethanes. These reactions proceed via formation of a chiral, non-racemic nickel benzyl intermediate. Transmetalation with arylboron nucleophiles and subsequent reductive elimination enable the formation of a variety of chiral 1,1-diarylethanes. The 1,1-diarylethane products from reactions of arylboronic acids containing electron-donating substituents are formed with typically greater than 90% ee, while the 1,1-diarylethanes generated from reactions of arylboronic acids containing electron-withdrawing groups are generated with typically less than 80% ee. These results are consistent with the rate of transmetalation with an arylboron nucleophile playing a key role in the enantioselectivity of these hydroarylation reactions. This mechanistic insight has led to the development of reactions of neo-pentylglycolate esters of arylboronic acids with vinylarenes that occur with higher enantioselectivities based on increased rates of transmetalation.
Preparation and Characterisation of a Bis-μ-Hydroxo-NiIII 2 Complex
Spedalotto, Giuseppe,Gericke, Robert,Lovisari, Marta,Farquhar, Erik R.,Twamley, Brendan,McDonald, Aidan R.
, p. 11983 - 11990 (2019/08/26)
Hydroxide-bridged high-valent oxidants have been implicated as the active oxidants in methane monooxygenases and other oxidases that employ bimetallic clusters in their active site. To understand the properties of such species, bis-μ-hydroxo-NiII 2 complex (1) supported by a new dicarboxamidate ligand (N,N′-bis(2,6-dimethyl-phenyl)-2,2-dimethylmalonamide) was prepared. Complex 1 contained a diamond core made up of two NiII ions and two bridging hydroxide ligands. Titration of the 1 e? oxidant (NH4)2[CeIV(NO3)6] with 1 at ?45 °C showed the formation of the high-valent species 2 and 3, containing NiIINiIII and NiIII 2 diamond cores, respectively, maintaining the bis-μ-hydroxide core. Both complexes were characterised using electron paramagnetic resonance, X-ray absorption, and electronic absorption spectroscopies. Density functional theory computations supported the spectroscopic assignments. Oxidation reactivity studies showed that bis-μ-hydroxide-NiIII 2 3 was capable of oxidizing substrates at ?45 °C at rates greater than that of the most reactive bis-μ-oxo-NiIII complexes reported to date.