Thiyl Radical Mediated Racemization of Nonactivated Aliphatic Amines
- 24 August 2006
- journal article
- Published by American Chemical Society (ACS) in The Journal of Organic Chemistry
- Vol. 71 (19) , 7288-7292
- https://doi.org/10.1021/jo061033l
Abstract
The racemization of nonactivated aliphatic amines has been mediated with alkanethiols and with methyl thioglycolate in the presence of AIBN. The process involves reversible H-abstraction at the chiral center, in a position α relative to nitrogen, by thiyl radical. The knowledge of the reaction enthalpy is critical to select the appropriate thiol. In the absence of experimental values, theoretical calculations of the α-C−H BDEs and the S−H BDE provide a useful guide.Keywords
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