Stereoselective two-carbon ring expansion of allylic amines via electronic control of palladium-promoted equilibria Dr Jonathan P. Knowles, Charlie P. Mikan, Aidan Matthews, Charlotte McIvor, Daniel
Harris, Paul G. Waddell Northumbria University, UK
Nitrogen-containing heterocycles represent a key class of bioactive molecule, featuring widely both in natural products and drug discovery. 1 The development of novel methodologies which provide access to such compounds is therefore a key goal for synthetic chemists, especially where such approaches provide stereoselective access to novel ring systems and chemical space. Herein we report 2 that the palladium-catalysed ring expansion of allylic amines enables the two-carbon ring expansion of 5- and 6-membered compounds 1 into their azepane and azocane homologues 2 . Conditions are mild and tolerant of a range of functional groups, and the process can proceed with a high degree of enantio-retention. The products are ideally functionalised to undergo a range of chemo- and stereo-selective processes, thereby providing rapid access to a range of modifiable polycyclic scaffolds as exemplified by amines 3 , 4 and 5 .
References 1. Vitaku, D. T. Smith and J. T. Njardarson, J. Med. Chem . 2014, 57 , 10257. 2. P. Mikan, A. Matthews, D. Harris, C. E. McIvor, P. Waddell and J. P. Knowles, doi.org/10.26434/chemrxiv-2023-5l255
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© The Author(s), 2023
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