ab initio calculations of complexes of group IVA tetrachlorides: I. Dynamics of complex formation of SiCl4 with pyridine

Фешин, В. П.; Фешина, Е. В.; Zhizhina, L. I.

doi:10.1134/s1070363206100112

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“…It is known that SiX 4 compounds can generate hexacoordinated complexes in the presence of 1,1-phenanthroline, 2,2′-bipyridine and pyridines [ 35 , 36 , 37 , 38 , 39 , 40 , 41 , 42 ]. Among them, only pyridines are able to generate trans -complexes with a 2:1 pyridine:Si ratio; therefore, we decided to synthesize a recognition system ( Scheme 5 a).…”

Section: Resultsmentioning

confidence: 99%

Novel Chiral Bis-Phosphoramides as Organocatalysts for Tetrachlorosilane-Mediated Reactions

et al. 2017

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The formation of novel chiral bidentate phosphoroamides structures able to promote Lewis base-catalyzed Lewis acid-mediated reactions was investigated. Two different classes of phosphoroamides were synthetized: the first class presents a phthalic acid/primary diamine moiety, designed with the aim to perform a self-assembly recognition process through hydrogen bonds; the second one is characterized by the presence of two phosphoroamides as side arms connected to a central pyridine unit, able to chelate SiCl4 in a 2:1 adduct. These species were tested as organocatalysts in the stereoselective allylation of benzaldehyde and a few other aromatic aldehydes with allyl tributyltin in the presence of SiCl4 with good results. NMR studies confirm that only pyridine-based phosphoroamides effectively coordinate tetrachlorosilane and may lead to the generation of a self-assembled entity that would act as a promoter of the reaction. Although further work is necessary to clarify and confirm the formation of the hypothesized adduct, the study lays the foundation for the design and the synthesis of chiral supramolecular organocatalysts.

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