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

doi:10.1055/s-0037-1611646

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

Pure And Applied Chemistry

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15 Citations (Scopus)

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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(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.

Original language	English
Pages (from-to)	1207-1215
Number of pages	9
Journal	Synthesis
Volume	51
Issue number	05
DOIs	https://doi.org/10.1055/s-0037-1611646
Publication status	Published - 15 Jan 2019

Keywords

metalation
gallium trans metal trapping
carbanions
cooperative effects
lithium
sodium

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10.1055/s-0037-1611646Licence: CC BY-NC-ND 4.0

McLellan-etal-Synthesis2018-Alkali-metal-effects-in-trans-metal-trapping-TMTFinal published version, 4.03 MBLicence: CC BY-NC-ND 4.0

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 = jan,

day = "15",

doi = "10.1055/s-0037-1611646",

language = "English",

volume = "51",

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journal = "Synthesis",

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TY - JOUR

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

T2 - comparing LiTMP with NaTMP in cooperative MTMP/Ga(CH2SiMe3)3 metalation reactions

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

U2 - 10.1055/s-0037-1611646

DO - 10.1055/s-0037-1611646

M3 - Article

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VL - 51

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JO - Synthesis

JF - Synthesis

IS - 05

ER -

Alkali metal effects in trans-metal-trapping (TMT): comparing LiTMP with NaTMP in cooperative MTMP/Ga(CH₂SiMe₃)₃ metalation reactions

Abstract

Keywords

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Towards a Paradigm Shift in the Principles and Practice of Polar Organometallic Chemistry

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Alkali metal effects in trans-metal-trapping (TMT): comparing LiTMP with NaTMP in cooperative MTMP/Ga(CH2SiMe3)3 metalation reactions

Abstract

Keywords

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Towards a Paradigm Shift in the Principles and Practice of Polar Organometallic Chemistry

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Alkali metal effects in trans-metal-trapping (TMT): comparing LiTMP with NaTMP in cooperative MTMP/Ga(CH₂SiMe₃)₃ metalation reactions