372191-55-4Relevant academic research and scientific papers
A new route to hindered tertiary amines
Yang,Wang,Li,Livant
, p. 6729 - 6733 (2001)
The Rh2(OAc)4-stabilized carbenoid derived from dimethyl diazomalonate has been found to insert into the N-H bond of sterically hindered secondary aliphatic amines to afford hindered tertiary aliphatic amines in quite satisfactory yields. For example dimethyl 2-(dicyclohexylamino)-propanedioate was formed in 85% yield from dicyclohexylamine, and the severely hindered dimethyl 2-(2,2,6,6-tetramethyl-1-piperidinyl)propanedioate was formed in 38% yield from 2,2,6,6-tetramethylpiperidine. The Rh2(OAc)4 - dimethyl diazomalonate reaction was found to work also for arylalkylamines and diarylamines. In these cases, small amounts of products resulting from formal insertion of the carbenoid into an aromatic C-H bond were detected. Substitution at ortho positions caused the yield of C-H insertion products to increase. Other diazo compounds, viz. ethyl diazoacetoacetate, 2-diazocyclohexane-1,3-dione, and 2-diazo-5,5-dimethylcyclohexane-1,3-dione, performed satisfactorily in Rh2(OAc)4-catalyzed reactions with arylalkylamines and diarylamines, but led to complicated reaction mixtures with dialkylamines.
Trialkylamines more planar at nitrogen than triisopropylamine in the solid state
Yang, Minmin,Albrecht-Schmitt, Thomas,Cammarata, Vince,Livant, Peter,Makhanu, David S.,Sykora, Richard,Zhu, Wei
scheme or table, p. 2671 - 2678 (2009/08/08)
A short synthesis of exceedingly congested amines, with insertion of a rhodium carbenoid into an N-H bond as the key step, is described. Trialkylamines such as 2-(diisopropylamino)propane-1,3-diol (8) and 2-(2,2,6,6-tetramethyl-1- piperidinyl)propane-1,3-
