19079-79-9Relevant academic research and scientific papers
Contra-thermodynamic Hydrogen Atom Abstraction in the Selective C-H Functionalization of Trialkylamine N-CH3 Groups
Barham, Joshua P.,John, Matthew P.,Murphy, John A.
supporting information, p. 15482 - 15487 (2016/12/09)
We report a simple one-pot protocol that affords functionalization of N-CH3 groups in N-methyl-N,N-dialkylamines with high selectivity over N-CH2R or N-CHR2 groups. The radical cation DABCO+?, prepared in situ by oxidation of DABCO with a triarylaminium salt, effects highly selective and contra-thermodynamic C-H abstraction from N-CH3 groups. The intermediates that result react in situ with organometallic nucleophiles in a single pot, affording novel and highly selective homologation of N-CH3 groups. Chemoselectivity, scalability, and recyclability of reagents are demonstrated, and a mechanistic proposal is corroborated by computational and experimental results. The utility of the transformation is demonstrated in the late-stage site-selective functionalization of natural products and pharmaceuticals, allowing rapid derivatization for investigation of structure-activity relationships.
Synthetic Approaches to Nortropanes and Nortrop-6-enes; Intramolecular Displacement by Nitrogen in 7-Membered Rings
Naylor, Antoinette,Howarth, Nicola,Malpass, John R.
, p. 451 - 468 (2007/10/02)
The synthesis of simple nortropane and nortrop-6-ene derivatives from cyclohepta-1,3-diene is described.The key intermediates are trans-1-amino-4-chloro-cycloheptanes and -cyclohept-2-enes which are derived efficiently from the corresponding cis-amino-alcohols and undergo intramolecular cyclisation.Corresponding derivatisation of cyclohexa- and cycloocta-1,3-dienes is explored and attempts to achieve Pd-catalysed cyclisation of 1-amino-4-acetoxy-derivatives is described.Nitrogen inversion data for selected nortropane derivatives are included. Key Words: nortropanes/enes; 1,4-disubstitute cyclohexanes, cycloheptanes, cyclooctanes and -enes; intramolecular cyclisation; slow nitrogen inversion.
A SIMPLE APPROACH TO NORTROPANE AND NORTROP-6-ENE DERIVATES
Bathgate, Antoinette,Malpass, John R.
, p. 5937 - 5940 (2007/10/02)
Intramolecular cyclisation of trans-1-(benzylamino)-4-chlorocycloheptane and hept-2-ene gives the corresponding 8-azabicyclo(3.2.1)octane (nortropane) and -oct-6-ene (nortrop-6-ene) derivatives respectively.Under appropriate conditions, cyclohept-1,3-diene is converted into nortropane in 75percent overall yield.
Hydroformylation of Nitrogen-Containing Cyclic Olefins via "in-situ" Rhodium-Phosphine Catalysts
Prokai-Tatrai, K.,Toeroes, S.,Heil, B.
, p. 231 - 236 (2007/10/02)
Hydroformylation of nitrogen-containing cyclic olefins (N-substituted nortropidines, N-methyl-1,2,3,6-tetrahydropyridine (THP)) with rhodium-PR3 catalysts prepared "in-situ" is reported.The nortropidines reacted rapidly when either trialkyl- or triaryl-type phosphines were used, and the regioselectivities were not significantly influenced by the nature of the phosphine.With the less basic THP the rates and selectivities were generally lower, and were influenced by the phosphine ligand and by the presence of added bases such as Et3N.
