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Ring Contraction of Saturated Cyclic Amines and Rearrangement of Acyclic Amines Through Their Corresponding Hydroxylamines.

Ring Contraction of Saturated Cyclic Amines and Rearrangement of Acyclic Amines Through Their Corresponding Hydroxylamines.

Authors :
Peng, Yi
Wang, Guoqiang
Klare, Hendrik F. T.
Oestreich, Martin
Source :
Angewandte Chemie. Oct2024, Vol. 136 Issue 40, p1-8. 8p.
Publication Year :
2024

Abstract

Compared to modifications at the molecular periphery, skeletal adjustments present greater challenges. Within this context, skeletal rearrangement technology stands out for its significant advantages in rapidly achieving structural diversity. Yet, the development of this technology for ring contraction of saturated cyclic amines remains exceedingly rare. While most existing methods rely on specific substitution patterns to achieve ring contraction, there is a persistent demand for a more general strategy for substitution‐free cyclic amines. To address this issue, we report a B(C6F5)3‐catalyzed skeletal rearrangement of hydroxylamines with hydrosilanes. This methodology, when combined with the N‐hydroxylation of amines, enables the regioselective ring contraction of cyclic amines and proves equally effective for rapid reorganization of acyclic amine skeletons. By this, the direct scaffold hopping of drug molecules and the strategic deletion of carbon atoms are achieved in a mild manner. Based on mechanistic experiments and density functional theory calculations, a possible mechanism for this process is proposed. [ABSTRACT FROM AUTHOR]

Details

Language :
English
ISSN :
00448249
Volume :
136
Issue :
40
Database :
Academic Search Index
Journal :
Angewandte Chemie
Publication Type :
Academic Journal
Accession number :
179808613
Full Text :
https://doi.org/10.1002/ange.202410483