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 Maria Gil-Negrete, David R. Armstrong, Alan R. Kennedy, Robert E. Mulvey, Eva Hevia

Research output: Contribution to journalArticle

1 Citation (Scopus)

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 metalate 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.
LanguageEnglish
Pages1207-1215
Number of pages9
JournalSynthesis
Volume51
Issue number05
DOIs
Publication statusPublished - 15 Jan 2019

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Alkali Metals
Alkali metals
Metals
Diamines
anisole
phenyllithium

Keywords

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

Cite this

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title = "Alkali metal effects in trans-metal-trapping (TMT): comparing LiTMP with NaTMP in cooperative MTMP/Ga(CH2SiMe3)3 metalation reactions",
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 metalate 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.",
keywords = "metalation, gallium trans metal trapping, carbanions, cooperative effects, lithium, sodium",
author = "Ross McLellan and Marina Uzelac and Bole, {Leonie J.} and Gil-Negrete, {Jose Maria} and Armstrong, {David R.} and Kennedy, {Alan R.} and Mulvey, {Robert E.} and Eva Hevia",
year = "2019",
month = "1",
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pages = "1207--1215",
journal = "Synthesis",
issn = "0039-7881",
publisher = "Georg Thieme Verlag",
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Alkali metal effects in trans-metal-trapping (TMT) : comparing LiTMP with NaTMP in cooperative MTMP/Ga(CH2SiMe3)3 metalation reactions. / McLellan, Ross; Uzelac, Marina; Bole, Leonie J.; Gil-Negrete, Jose Maria; Armstrong, David R.; Kennedy, Alan R.; Mulvey, Robert E.; Hevia, Eva.

In: Synthesis, Vol. 51, No. 05, 15.01.2019, p. 1207-1215.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Alkali metal effects in trans-metal-trapping (TMT)

T2 - Synthesis

AU - McLellan, Ross

AU - Uzelac, Marina

AU - Bole, Leonie J.

AU - Gil-Negrete, Jose Maria

AU - Armstrong, David R.

AU - Kennedy, Alan R.

AU - Mulvey, Robert E.

AU - Hevia, Eva

PY - 2019/1/15

Y1 - 2019/1/15

N2 - 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 metalate 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.

AB - 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 metalate 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.

KW - metalation

KW - gallium trans metal trapping

KW - carbanions

KW - cooperative effects

KW - lithium

KW - sodium

UR - https://www.thieme.de/de/synthesis/journal-information-55920.htm

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DO - 10.1055/s-0037-1611646

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