Stereospecific Synthesis of α‑Amino Allylsilane Derivatives through a [3,3]-Allyl Cyanate Rearrangement. Mild Formation of Functionalized Disiloxanes

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 th...

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Bibliographic Details
Published in:Journal of organic chemistry 2016-06, Vol.81 (11), p.4633-4644
Main Authors: Henrion, Sylvain, Carboni, Bertrand, Cossío, Fernando P, Roisnel, Thierry, Villalgordo, Jose M, Carreaux, François
Format: Article
Language:English
Subjects:
Chemical Sciences
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Summary: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.
ISSN:0022-3263
1520-6904
DOI:10.1021/acs.joc.6b00505