Silylation products of cyclic tri-aminal carbanions and their lithiation

Sicking C, Mix A, Neumann B, Stammler H-G, Mitzel NW (2012)
Dalton Transactions 41(1): 104-111.

Zeitschriftenaufsatz | Veröffentlicht | Englisch
 
Download
Es wurden keine Dateien hochgeladen. Nur Publikationsnachweis!
Abstract / Bemerkung
The structure of 1,3,5-trimethyl-1,3,5-triaza-cyclohexane (TMTAC) was determined by single crystal X-ray diffraction and compared with earlier gas-phase data. It shows a preference for an aee-conformation in all phases. Lithiated TMTAC, [(RLi)(2)center dot(RH)] (1) (R = 2,4,6-trimethyl-2,4,6-triazacyclohex- 1-yl), was reacted with Et(3)SiCl, Ph(3)SiCl and PhMe(2)SiCl to afford the substituted silanes Et(3)SiR (1), Ph(3)SiR (2) and PhMe(2)SiR (3) in moderate yields. They were characterised by NMR spectroscopy ((1)H, (13)C, (29)Si). 1 reacts with Me(2)SiCl(2) and Ph(2)SiCl(2) to give Me(2)SiR(2) (5) and Ph(2)SiR(2) (6) which were characterised by NMR spectroscopy. 5 was also identified by crystal structure determination. Analogous triple substitution could not be observed by employing trichlorosilanes. Quantumchemical calculations explain this by sterical overcrowding of the silicon atom. The reaction of 1 with SiCl(4) did not yield fourfold substitution but a formal insertion product of SiCl(2) into a C-N bond of the TMTAC ring (2,4,6-trimethyl-2,4,6-triaza-1,1-dichloro-1-sila-cycloheptane, 7) in very small quantities. It was identified by X-ray crystallography and shows an intramolecular Si center dot center dot center dot N dative bond. The reactions of (3) and (5) with n-butyl lithium afforded lithiation of the silicon bound methyl groups in both cases. The products, 8 and 9, were characterised by NMR spectroscopy ((1)H, (13)C, (29)Si), 8 was also characterised by X-ray crystallography.
Erscheinungsjahr
2012
Zeitschriftentitel
Dalton Transactions
Band
41
Ausgabe
1
Seite(n)
104-111
ISSN
1477-9226
eISSN
1477-9234
Page URI
https://pub.uni-bielefeld.de/record/2454681

Zitieren

Sicking C, Mix A, Neumann B, Stammler H-G, Mitzel NW. Silylation products of cyclic tri-aminal carbanions and their lithiation. Dalton Transactions. 2012;41(1):104-111.
Sicking, C., Mix, A., Neumann, B., Stammler, H. - G., & Mitzel, N. W. (2012). Silylation products of cyclic tri-aminal carbanions and their lithiation. Dalton Transactions, 41(1), 104-111. doi:10.1039/c1dt10943j
Sicking, Constantin, Mix, Andreas, Neumann, Beate, Stammler, Hans-Georg, and Mitzel, Norbert W. 2012. “Silylation products of cyclic tri-aminal carbanions and their lithiation”. Dalton Transactions 41 (1): 104-111.
Sicking, C., Mix, A., Neumann, B., Stammler, H. - G., and Mitzel, N. W. (2012). Silylation products of cyclic tri-aminal carbanions and their lithiation. Dalton Transactions 41, 104-111.
Sicking, C., et al., 2012. Silylation products of cyclic tri-aminal carbanions and their lithiation. Dalton Transactions, 41(1), p 104-111.
C. Sicking, et al., “Silylation products of cyclic tri-aminal carbanions and their lithiation”, Dalton Transactions, vol. 41, 2012, pp. 104-111.
Sicking, C., Mix, A., Neumann, B., Stammler, H.-G., Mitzel, N.W.: Silylation products of cyclic tri-aminal carbanions and their lithiation. Dalton Transactions. 41, 104-111 (2012).
Sicking, Constantin, Mix, Andreas, Neumann, Beate, Stammler, Hans-Georg, and Mitzel, Norbert W. “Silylation products of cyclic tri-aminal carbanions and their lithiation”. Dalton Transactions 41.1 (2012): 104-111.

30 References

Daten bereitgestellt von Europe PubMed Central.


Seyferth, J. Org. Chem. 24(), 1959

Köhler, Chem. Ber. 120(), 1987

Gessner, Angew. Chem. 119(), 2007

Gessner, Angew. Chem. Int. Ed. Engl. 46(), 2007

Arnold, J. Chem. Soc., Dalton Trans. (), 2002

Schlosser, Angew. Chem. 85(), 1973

Schlosser, Angew. Chem., Int. Ed. Engl. 12(), 1973

Bauer, J. Am. Chem. Soc. 114(), 1992

Strohmann, Angew. Chem. 119(), 2007

Strohmann, Angew. Chem. Int. Ed. Engl. 46(), 2007

Karsch, Chem. Ber. 129(), 1996

Bojer, Angew. Chem. 119(), 2007

Köhn, Chem. Ber. 129(), 1996

Kamps, Chem. Commun. (), 2009

Kamps, Chem.–Eur. J. 15(), 2009

Strohmann, Chem.–Asian J. 3(), 2008

Kamps, Dalton Trans. (), 2009
Three different product types from reactions of lithiated cyclic aminals with trivalent organometal chlorides.
Hellmann BJ, Kamps I, Mix A, Neumann B, Stammler HG, Mitzel NW., Chem. Commun. (Camb.) 46(35), 2010
PMID: 20714557

Jones, J. Chem. Soc. (B) (), 1970

Bushweller, J. Am. Chem. Soc. 96(), 1974

Hutchins, J. Am. Chem. Soc. 90(), 1968

Harris, J. Am. Chem. Soc. 119(), 1997

Jewett, J. Am. Chem. Soc. 122(), 2000

Zverev, Russ. J. Phys. Chem. A 81(), 2007

Sicking, 2010

Anderson, J. Chem. Soc., Dalton Trans. (), 1987

Mitzel, Z. Naturforsch. 58b(), 2003

Lindfors, Acta Crystallogr., Sect. C: Cryst. Struct. Commun. 54(), 1998

Sheldrick, Acta Crystallogr., Sect. A: Found. Crystallogr. A64(), 2008
Export

Markieren/ Markierung löschen
Markierte Publikationen

Open Data PUB

Web of Science

Dieser Datensatz im Web of Science®
Quellen

PMID: 22075546
PubMed | Europe PMC

Suchen in

Google Scholar