名称:
Synthesis of an alkylmagnesium amide and interception of a ring-opened isomer of the important utility amide 2,2,6,6-tetramethylpiperidide (TMP)
摘要:
Two new magnesium complexes containing the important utility amide 2,2,6,6-tetramethylpiperidide (TMP) have been synthesised. Treating the magnesium bis(alkyl) reagent (Me3SiCH2)(2)Mg with a molar equivalent of TMP(H) in hydrocarbon medium produces the dimeric alkylmagnesium amide complex [(Me3SiCH2) Mg(mu-TMP)](2) 2, which was isolated in high yield. X-ray crystallography revealed that 2 was an unsymmetrical dimer as unusually the two TMP ligands adopt different conformations - one a chair, the other a twisted boat. Solution studies (multinuclear NMR and DOSY NMR spectroscopies) show that 2 undergoes a monomerisation and Schlenk equilibrium in d(8)-THF. When (Me3SiCH2)(2)Mg was reacted with two molar equivalents of TMP(H) in hydrocarbon medium [in an effort to prepare Mg(TMP)(2)] a crystalline sample of a surprising product, a tetranuclear triheteroanionic amide-alkoxide- amidoalkene [(TMP)Mg(mu-TMP){mu-N(H)C(Me)(2)CH2CH2CH2C(Me) = CH2}Mg(mu-OCH2SiMe3)](2) 3 was obtained. Complex 3 contains two unexpected anions, namely the alkoxide produced via oxygen insertion into a Mg-C bond, and the primary amidoalkene which is produced via ring opening of the TMP anion. (C) 2013 Elsevier B.V. All rights reserved.