Simple synthetic routes to regioselectively deuterated tris[2-(dimethylamino)ethyl]amine (Me6TREN) variants are described. Imine formation with formaldehyde-d2 from tris(2-aminoethyl)amine (TREN) and subsequent reductions with NaBD4 afforded N[CH2CH2N(CD3)2]3 or d18-Me6TREN in 79 % yield. A trisubstitution protocol from 2-bromo-N,N-dimethylacetamide and ammonium carbonate and subsequent reduction of the N(CH2CONMe2)3 intermediate by lithium aluminum deuteride has afforded N[CH2CD2N(CH3)2]3 or (d6-arm)-Me6TREN in three steps and 52 % overall yield. A similar protocol from 2-bromo-N,N-dimethyl-d2-acetamide, obtained in two steps from d4-acetic acid, with reduction of the N(CD2CONMe2)3 intermediate by lithium aluminum hydride has afforded N[CD2CH2N(CH3)2]3 or (d6-cap)-Me6TREN in four steps and 13 % overall yield from CD3COOD.

Financial support from NSF (CHE 2000391) is acknowledged. We also thank the CNRS (Centre National de la Recherche Scientifique) for support through the International Research Project (IRP) "Laboratory for Coordination Chemistry for Controlled Radical Polymerization" (LCC-CRP). J. S. gratefully acknowledges support by the Chateaubriand Fellowship of the Office for Science & Technology of the Embassy of France in the United States. A.G. acknowledges financial support in the form of the post-doctoral fellowship (Polish National Agency for Academic Exchange - Bekker Programme no. PPN/BEK/2018/1/00261; Polish-U.S. Fulbright Commission - Senior Award no. PL/2019/SR/41) and SONATA grant UMO-2020/39/D/ST4/01182 from National Science Centre, Poland.