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Abstract - ISCC11

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Exploiting Multicomponent Reagents in Synthesis:
Stepwise vs Synchronised Cooperative Behaviours
Eva Hevia
WestCHEM, University of Strathclyde, 295 Cathedral Street, Glasgow, UK
Eva.hevia@strath.ac.uk
Multicomponent bimetallic organometallic reagents are capable of producing new
chemistry irreproducible by either of their single organometallic components.[1]
However, recent work[2] has revealed that such heterobimetallic reagents do not
necessarily need to form mixed-metal compounds in order to exhibit this unique
cooperative behaviour, as they can alternatively operate in a stepwise process.
This talk firstly reviews our new results using cooperative bimetallics to promote
deprotonative metallations, operating either in a synchronised or stepwise manner.
These approaches have established novel ways to trap dianionic NHC (Nheterocyclic carbene) fragments in reactions of unprecedented chemoselectivity (1 in
Figure)3a and to access elusive main group abnormal NHC complexes3b (2 in Figure).
Secondly, the opening applications of mixed ammonium-magnesiate and lithiate salts
in Green Chemistry will be revealed through addition reactions of Grignard reagents
to ketones under air and at room temperature using Deep Eutectic Solvents.4
TMP
TMP
Dipp
N
N
[Na4Mg2(TMP)6(nBu)2]
concerted cooperation
Mg
1 TMP
Na
2
Dipp
Dipp
1. LiR
stepwise
2. GaR3 cooperation
R
R Ga
N
R
Dipp
iPr
N
Dipp
Na
N
N
1
iPr
Na
Na
trapping of
NHC dianion
TMP
Mg
TMP
TMP
Dipp
Dipp
N
Na
iPr
N
iPr
Na
N
MeOH
Scheme 2
R
N H
Ga
Li(THF) 3
R
abnormal
Dipp
R
NHC complex
2
R= CH2SiMe3; TMP= 2,2,6,6-tetramethylpiperdide
References:
1. F. Mongin, A. Harrison-Marchand, Chem. Rev. 2013, 113, 7563.
2. (a) S. E. Baillie, T. D. Bluemke, W. Clegg, A. R. Kennedy, J. Klett, L. Russo, M. de Tullio, E. Hevia
Chem. Commun. 2014, 50, 12859. (b) D. R. Armstrong, E. Crosbie, E. Hevia, R. E. Mulvey, D. L.
Ramsay, S. D. Robertson, Chem. Sci. 2014, 5, 3031.
3. (a) M. Uzelac, A. Hernán-Gómez, D. R. Armstrong, A. R. Kennedy, E. Hevia, Chem. Sci. 2015, 6,
5719. (b) A. Martínez, M. A. Fuentes, A. Hernán-Gómez, E. Hevia, A. R. Kennedy, R. E. Mulvey, C. T.
O'Hara, Angew. Chem. Int. Ed. 2015, 54, 14075.
4. (a) C. Vidal, J. Garcia-Alvarez, A. Hernan-Gomez, A. R. Kennedy, E. Hevia, Angew. Chem. Int. Ed.
2014, 53, 5969. (b) V. Capriati, J. Garcia-Alvarez, E. Hevia, Eur. J. Org. Chem., 2015, 6779
"11th International Symposium on Carbanion Chemistry"
17-21 July 2016, Rouen, Normandy, France
Rouen, Normandy, France
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