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.

(Click here to request a copy from the OU Author.)

DOI (Digital Object Identifier) Link:	http://dx.doi.org/doi:10.1007/s10593-012-0949-7
Google Scholar:	Look up in Google Scholar

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.

Item Type:	Journal Article
Copyright Holders:	2012 Springer Science+Business Media, Inc.
ISSN:	1573-8353
Funders:	Russian Foundation for Fundamental Investigations (projects Nos. 09-03-00669, 10-03-00824, and 11-03-00655)
Academic Unit/Department:	Other Departments > Other Departments Science > Life, Health and Chemical Sciences Science
Item ID:	34656
Depositing User:	Peter Taylor
Date Deposited:	24 Oct 2012 11:25
Last Modified:	22 Nov 2012 17:12
URI:	http://oro.open.ac.uk/id/eprint/34656

Actions (login may be required)

	View Item
	Public: Report issue / request change

Policies | Disclaimer