Please use this identifier to cite or link to this item: http://dx.doi.org/10.14279/depositonce-14798
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Main Title: Mild reductive rearrangement of oximes and oxime ethers to secondary amines with hydrosilanes catalyzed by B(C6F5)3
Author(s): Fang, Huaquan
Wang, Guoqiang
Oestreich, Martin
Type: Article
URI: https://depositonce.tu-berlin.de/handle/11303/16024
http://dx.doi.org/10.14279/depositonce-14798
License: https://creativecommons.org/licenses/by/3.0/
Abstract: The strong boron Lewis acid tris(pentafluorophenyl)borane, B(C6F5)3, has been found to catalyze the reductive rearrangement of oximes and their ether derivatives at room temperature with hydrosilanes as the reducing agents. Cyclic substrates undergo ring enlargement, and the secondary amine products are generally formed in good yields. Control experiments combined with a DFT computational analysis of the reaction mechanism suggest that there are three energetically accessible reaction pathways (paths A–C), either or not involving hydroxylamine derivatives. Paths A and B proceed through the intermediacy of a common N,O-bissilylated hydroxylamine, and the ring-expanding rearrangement yields an iminium ion. With no intermediate at the hydroxylamine oxidation level (path C), the reaction mechanism resembles that of the Beckmann rearrangement where an O-silylated oxime converts into a nitrilium ion. The reduction–rearrangement sequence (paths A and B) is slightly preferred over the rearrangement–reduction order of events (path C), especially at ambient temperature.
Subject(s): catalysis
reaction
reductive rearrangement
oxime
oxime ethers
Issue Date: 1-Apr-2021
Date Available: 29-Dec-2021
Language Code: en
DDC Class: 540 Chemie und zugeordnete Wissenschaften
Sponsor/Funder: TU Berlin, Open-Access-Mittel – 2021
Journal Title: Organic Chemistry Frontiers
Publisher: Royal Society of Chemistry (RSC)
Volume: 8
Issue: 13
Publisher DOI: 10.1039/d1qo00251a
Page Start: 3280
Page End: 3285
EISSN: 2052-4129
ISSN: 2052-4110
TU Affiliation(s): Fak. 2 Mathematik und Naturwissenschaften » Inst. Chemie » FG Organische Chemie / Synthese und Katalyse
Appears in Collections:Technische Universität Berlin » Publications

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