CC BY-ND-NC 4.0 · Synthesis 2019; 51(05): 1207-1215
DOI: 10.1055/s-0037-1611646
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Alkali Metal Effects in Trans-Metal-Trapping (TMT): Comparing LiTMP with NaTMP in Cooperative MTMP/Ga(CH2SiMe3)3 Meta­lation Reactions

Ross McLellan
,
Marina Uzelac
,
Leonie J. Bole
,
Jose María Gil-Negrete
,
David R. Armstrong
,
Alan R. Kennedy
,
WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow G1 1XL, UK   Email: r.e.mulvey@strath.ac.uk   Email: eva.hevia@strath.ac.uk
,
WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow G1 1XL, UK   Email: r.e.mulvey@strath.ac.uk   Email: eva.hevia@strath.ac.uk
› Author Affiliations
We thank the European Research Council (ERC StG, MixMetApps) and the EPSRC (EP/N011384/1) for their generous sponsorship of this research.
Further Information

Publication History

Received: 30 November 2018

Accepted: 05 December 2018

Publication Date:
15 January 2019 (online)


Published as part of the 50 Years SYNTHESIS – Golden Anniversary Issue

Abstract

Stepwise metalation and trapping, so called trans-metal-trapping (TMT), of anisole is studied using LiTMP as base and Ga(CH2SiMe3)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.

Supporting Information

 
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