7446-94-8Relevant articles and documents
O2-Mediated Oxidation of Aminoboranes through 1,2-N Migration
Rauser, Marian,Warzecha, Daniel P.,Niggemann, Meike
supporting information, p. 5903 - 5907 (2018/05/14)
In analogy to the classical reaction of C?B bonds with peroxides, the first oxidative functionalization of aminoboranes through a 1,2-N migration was realized. Readily available aliphatic nitro compounds are thereby transformed into N- and O-functionalized hydroxylamines in a single synthetic operation. Addition of hazardous peroxides is avoided. Instead, the insertion of O2, as the terminal oxidant, into Zn?C bonds provides the necessary peroxides. The required zinc organyls, in turn, are formed through a boron-to-zinc exchange, from an organoboronic ester byproduct of the nitro-to-aminoborane transformation.
Toward total spontaneous resolution of sec-Butylzinc complexes
Lennartson, Anders,Hedstroem, Anna,Hakansson, Mikael
, p. 177 - 183 (2010/03/04)
Di-sec-butylzinc has been used to synthesize [Zn(s-Bu)2L 2] complexes, where L denotes amine ligands: e.g., pyridine (py), 2-picoline (2-pic), and 3-picoline (3-pic). The crystal structures of [Zn(sBu)2(py)2] (1), [Zn(s-Bu)2(2-pic) 2] (2), and [Zn(s-Bu)2(3-pic)2] (3) were determined. Reaction of di-sec-butylzinc with the bidentate amine ligands N, N, N', N' -tetramethylethylenediamine (TMEDA) and N, N, N', N' - tetraethylethylenediamine (TEEDA) afforded the chiral complexes [Zn(s-Bu) 2(tmeda)] (4) and [Zn(s-Bu)2(teeda)] (5); their crystal structures were determined. Since they coordinate two s-Bu groups each, complexes 1-5 may exist both as chiral and meso molecules in solution, but the crystalline complexes were found to be exclusively chiral. The enantiomerization rate of 1-5 in benzene was found to be slow on the NMR time scale. Chiral crystalline complexes containing the Zn(s-Bu)2 moiety are of particular interest, since they display reactive chirogenic α-carbon atoms. The identification of a Zn(s-Bu)2 complex such as 1-5, which crystallized as a conglomerate of chiral crystals, would afford a simple and cheap way to optical resolution of a chiral organometallic reagent, without the need to use enantiopure ligands. Using preferential crystallization, it should be possible to perform total spontaneous resolution, which may be regarded as a form of absolute asymmetric synthesis. However, all complexes isolated so far, including the dinuclear alkylzinc amide [Zn(s-Bu)(Me2N(CH 2)2NH)]2 (6), crystallize in centrosymmetric space groups. As a remedy, recrystallization of Zn(s-Bu)2 complexes from different solvents was studied: in at least two cases, viz. [Zn(s-Bu) 2(3-pic)2] ? C7H8 (7) and [Zn(s-Bu)2(3,5-lut)2] ? C7H8 (8), it was found that recrystallization from toluene gave rise to clathrates. 2009 American Chemical Society.
GEMISCHTE ORGANOZINKVERBINDUNGEN DURCH AUSTAUSCHREAKTIONEN VON DIORGANOZINKVERBINDUNGEN
Nehl, Hans,Scheidt, Walter R.
, p. 1 - 8 (2007/10/02)
The exchange of organyl groups between various diorganozinc compounds, R12Zn (R1=CHMe2 (1), CH2(CH2)2Me (2), CH2C(Me)=CH2 (3), CH2CH=CHMe (4)) and R22Zn (R2=Et (5), CH(Me)Et (6), CH2(CH2)3Me (7), CMe3 (8), Menth
