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Stereospecific Synthesis of α‑Amino Allylsilane Derivatives through a [3,3]-Allyl Cyanate Rearrangement. Mild Formation of Functionalized Disiloxanes
Ist Teil von
Journal of organic chemistry, 2016-06, Vol.81 (11), p.4633-4644
Ort / Verlag
United States: American Chemical Society
Erscheinungsjahr
2016
Link zum Volltext
Quelle
Alma/SFX Local Collection
Beschreibungen/Notizen
An efficient asymmetric synthesis of α-amino allylsilane derivatives is reported. The strategy is based on a [3,3]-allyl cyanate sigmatropic rearrangement from enantioenriched γ-hydroxy alkenylsilyl compounds. The isocyanate intermediate can be trapped by several nucleophiles, opening the way for the preparation of unknown chiral functionalized compounds such as the α-ureido allylsilanes as well as carbamate derivatives. A computational study was conducted to rationalize the complete 1,3-chirality transfer of this kind of rearrangement. Moreover, starting from products bearing a phenyldimethyl silyl substituent, the α-amino silane derivatives or the corresponding disiloxanes can be obtained under hydrogenation conditions in an exclusive way according to the used catalyst.