Alkali Metal Effects in Trans-Metal-Trapping (TMT): Comparing LiTMP with NaTMP in Cooperative MTMP/Ga(CH                         2                         SiMe                         3                         )                         3                          Metalation Reactions

Ross McLellan; Marina Uzelac; Leonie J. Bole; Jose María Gil-Negrete; David R. Armstrong; Alan R. Kennedy; Robert E. Mulvey; Eva Hevia

doi:10.1055/s-0037-1611646

Alkali Metal Effects in Trans-Metal-Trapping (TMT): Comparing LiTMP with NaTMP in Cooperative MTMP/Ga(CH ₂ SiMe ₃ ) ₃ Metalation Reactions

Ross McLellan, Marina Uzelac, Leonie J. Bole, Jose María Gil-Negrete, David R. Armstrong, Alan R. Kennedy, Robert E. Mulvey, Eva Hevia

Department of Chemistry

University of Strathclyde

Research output: Contribution to journal › Review article › peer-review

14 Citations (SciVal)

Abstract

Stepwise metalation and trapping, so called trans-metal-trapping (TMT), of anisole is studied using LiTMP as base and Ga(CH ₂ SiMe ₃ ) ₃ as trap. The isolated 'trapped' intermediate is also assessed in C-C bond forming reactions, highlighting the inherent advantages and remaining challenges of this system. The same base trap mixture is found to metallate N-Me bonds of the diamines TMEDA and PMDETA. Comparative studies replacing LiTMP by NaTMP have found significant alkali metal effects on the extent of both base-trap cocomplexation and onward reactivities of TMT products.

Original language	English
Pages (from-to)	1207-1215
Number of pages	9
Journal	Synthesis (Germany)
Volume	51
Issue number	5
DOIs	https://doi.org/10.1055/s-0037-1611646
Publication status	Published - 15 Jan 2019

Bibliographical note

Funding Information:
We thank the European Research Council (ERC StG, MixMetApps) and the EPSRC (EP/N011384/1) for their generous sponsorship of this research. European Research Council (ERCStG, MixMetApps) Engineering and Physical Sciences Research Council (EP/N011384/1)

Keywords

carbanions
cooperative effects
gallium trans-metal-trapping
lithium
metalation
sodium

ASJC Scopus subject areas

Catalysis
Organic Chemistry

Access to Document

10.1055/s-0037-1611646Licence: CC BY-NC-ND

Cite this

McLellan, R., Uzelac, M., Bole, L. J., Gil-Negrete, J. M., Armstrong, D. R., Kennedy, A. R., Mulvey, R. E., & Hevia, E. (2019). Alkali Metal Effects in Trans-Metal-Trapping (TMT): Comparing LiTMP with NaTMP in Cooperative MTMP/Ga(CH ₂ SiMe ₃ ) ₃ Metalation Reactions. Synthesis (Germany), 51(5), 1207-1215. https://doi.org/10.1055/s-0037-1611646

Alkali Metal Effects in Trans-Metal-Trapping (TMT): Comparing LiTMP with NaTMP in Cooperative MTMP/Ga(CH ₂ SiMe ₃ ) ₃ Metalation Reactions. / McLellan, Ross; Uzelac, Marina; Bole, Leonie J. et al.
In: Synthesis (Germany), Vol. 51, No. 5, 15.01.2019, p. 1207-1215.

Research output: Contribution to journal › Review article › peer-review

McLellan, R, Uzelac, M, Bole, LJ, Gil-Negrete, JM, Armstrong, DR, Kennedy, AR, Mulvey, RE & Hevia, E 2019, 'Alkali Metal Effects in Trans-Metal-Trapping (TMT): Comparing LiTMP with NaTMP in Cooperative MTMP/Ga(CH ₂ SiMe ₃ ) ₃ Metalation Reactions', Synthesis (Germany), vol. 51, no. 5, pp. 1207-1215. https://doi.org/10.1055/s-0037-1611646

McLellan R, Uzelac M, Bole LJ, Gil-Negrete JM, Armstrong DR, Kennedy AR et al. Alkali Metal Effects in Trans-Metal-Trapping (TMT): Comparing LiTMP with NaTMP in Cooperative MTMP/Ga(CH ₂ SiMe ₃ ) ₃ Metalation Reactions. Synthesis (Germany). 2019 Jan 15;51(5):1207-1215. doi: 10.1055/s-0037-1611646

McLellan, Ross ; Uzelac, Marina ; Bole, Leonie J. et al. / Alkali Metal Effects in Trans-Metal-Trapping (TMT) : Comparing LiTMP with NaTMP in Cooperative MTMP/Ga(CH ₂ SiMe ₃ ) ₃ Metalation Reactions. In: Synthesis (Germany). 2019 ; Vol. 51, No. 5. pp. 1207-1215.

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abstract = " Stepwise metalation and trapping, so called trans-metal-trapping (TMT), of anisole is studied using LiTMP as base and Ga(CH 2 SiMe 3 ) 3 as trap. The isolated 'trapped' intermediate is also assessed in C-C bond forming reactions, highlighting the inherent advantages and remaining challenges of this system. The same base trap mixture is found to metallate N-Me bonds of the diamines TMEDA and PMDETA. Comparative studies replacing LiTMP by NaTMP have found significant alkali metal effects on the extent of both base-trap cocomplexation and onward reactivities of TMT products.",

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