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

15 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)

Funding

Merit Award, Royal Society Leverhulme Trust Senior Research Fellowship, GDCh Arfvedson Schlenk Prize, and a Humboldt Research Award. A Fellow of both the Royal Society of Edinburgh and Royal So ciety of Chemistry, he has published ap proaching 300 papers. We thank the European Research Council (ERC StG, MixMetApps) and the EPSRC (EP/N011384/1) for their generous sponsorship of this research.EuropeanResearchCouncil(ERCStG,MixMetApps)EngineeringandPhysicalSciencesResearchCouncil (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.

@article{3c7258fe498a43fa9067eda353e88d1a,

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

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.",

keywords = "carbanions, cooperative effects, gallium trans-metal-trapping, lithium, metalation, sodium",

author = "Ross McLellan and Marina Uzelac and Bole, {Leonie J.} and Gil-Negrete, {Jose Mar{\'i}a} and Armstrong, {David R.} and Kennedy, {Alan R.} and Mulvey, {Robert E.} and Eva Hevia",

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) ",

year = "2019",

month = jan,

day = "15",

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

language = "English",

volume = "51",

pages = "1207--1215",

journal = "Synthesis (Germany)",

issn = "0039-7881",

publisher = "Georg Thieme Verlag",

number = "5",

}

TY - JOUR

T1 - Alkali Metal Effects in Trans-Metal-Trapping (TMT)

T2 - Comparing LiTMP with NaTMP in Cooperative MTMP/Ga(CH 2 SiMe 3 ) 3 Metalation Reactions

AU - McLellan, Ross

AU - Uzelac, Marina

AU - Bole, Leonie J.

AU - Gil-Negrete, Jose María

AU - Armstrong, David R.

AU - Kennedy, Alan R.

AU - Mulvey, Robert E.

AU - Hevia, Eva

N1 - 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)

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(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.

AB - 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.

KW - carbanions

KW - cooperative effects

KW - gallium trans-metal-trapping

KW - lithium

KW - metalation

KW - sodium

UR - http://www.scopus.com/inward/record.url?scp=85061917201&partnerID=8YFLogxK

U2 - 10.1055/s-0037-1611646

DO - 10.1055/s-0037-1611646

M3 - Review article

AN - SCOPUS:85061917201

SN - 0039-7881

VL - 51

SP - 1207

EP - 1215

JO - Synthesis (Germany)

JF - Synthesis (Germany)

IS - 5

ER -