Pentacoordinated chlorosilanes with C,O-chelate ligands derived from N-methyl-N'-organosulfonyl-prolinamides

Nikolin, A. A.; Arkhipov, D. E.; Shipov, A. G.; Kramarova, E. P.; Koval'chuk, N. A.; Korlyukov, A. A.; Negrebetsky, V. V.; Baukov, Yu. I.; Bassindale, Alan; Taylor, P. G.; Bowden, A. and Bylikin, S. Yu. (2012). Pentacoordinated chlorosilanes with C,O-chelate ligands derived from N-methyl-N'-organosulfonyl-prolinamides. Chemistry of Heterocyclic Compounds, 47(12) pp. 1565–1583.

DOI: https://doi.org/10.1007/s10593-012-0949-7

Abstract

The reaction of amides RSO₂-Pro-NHMe with ClCH₂SiMe₂Cl in the presence of (Me₃Si)₂NH gave pentacoordinated chlorosilanes RSO₂-Pro-N(Me)CH₂SiMe₂Cl with an organosulfonyl group (R = Me, Ph, 4-ClC₆H₄, 4-BrC₆H₄, 4-MeC₆H₄, and 4-O₂NC₆H₄) attached to the proline nitrogen atom. An alternative method for the preparation of these compounds comprises the cyclosilylmethylation of proline methylamide by dimethylchloromethylchlorosilane to give the previously unreported heterocyclic 2-sila-5-piperazinone system in the first step. The bicyclic silacyclane synthesized is 2-sila5-piperazinone condensed with a proline residue. The action of sulfonyl chlorides RSO₂Cl leads to cleavage of the sila ring Si-N bond to give the desired chlorosilanes. The hydrolysis of these products, depending on the reaction conditions, gives either silyloxonium chlorides [RSO₂-ProN(Me)CH₂SiMe₂OH₂]Cl or disiloxanes [RSO₂-Pro-N(Me)CH₂SiMe₂]₂O. X-ray diffraction structural analysis showed that the silicon atom in the chlorides and silyloxonium chlorides is pentacoordinated due to an intramolecular O→Si bond and has distorted trigonal-bipyrimidal configuration. Si-²⁹ NMR spectroscopy showed that the disiloxanes and bicyclic sila-5-piperazinone have a tetracoordinated silicon atom.

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