Sterically facilitated meta-lithiation of arenes, containing electron-donating groups

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Sterically facilitated meta-lithiation of arenes, containing electron-donating groups. / Antonov, Alexander S.; Bardakov, Victor G.; Mulloyarova, Valeriia V.

In: Journal of Organometallic Chemistry, Vol. 906, 121068, 15.01.2020.

Research output: Contribution to journal › Article › peer-review

BibTeX

@article{ce485504d7b849148b685528c6ae5db1,

title = "Sterically facilitated meta-lithiation of arenes, containing electron-donating groups",

abstract = "The influence of the bulky trimethylsilyl substituent on the selectivity of metallation of dimethylaniline, anisole and 1-dimethylaminonaphthalene is studied. The neighboring SiMe3 group forces dimethylamino and methoxy groups to occupy a conformation with an unshared electron pair turned towards silicon atom. This forced conformation prevents NMe2 and OMe groups from providing the DOM-effect, thus facilitating meta-metallation with the use of bulky LiCKOR. While the inverted NMe2 group completely suppresses ortho-metallation, the less bulky and more electron withdrawing OMe group demonstrates more rotation freedom allowing selective ortho-metallation with smaller reagents such as n-BuLi or tert-BuLi.",

keywords = "Aniline, Lithiation, Silicon, Sterical effect, PROTON SPONGE, METALATION",

author = "Antonov, {Alexander S.} and Bardakov, {Victor G.} and Mulloyarova, {Valeriia V.}",

year = "2020",

month = jan,

day = "15",

doi = "10.1016/j.jorganchem.2019.121068",

language = "English",

volume = "906",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier",

}

RIS

TY - JOUR

T1 - Sterically facilitated meta-lithiation of arenes, containing electron-donating groups

AU - Antonov, Alexander S.

AU - Bardakov, Victor G.

AU - Mulloyarova, Valeriia V.

PY - 2020/1/15

Y1 - 2020/1/15

N2 - The influence of the bulky trimethylsilyl substituent on the selectivity of metallation of dimethylaniline, anisole and 1-dimethylaminonaphthalene is studied. The neighboring SiMe3 group forces dimethylamino and methoxy groups to occupy a conformation with an unshared electron pair turned towards silicon atom. This forced conformation prevents NMe2 and OMe groups from providing the DOM-effect, thus facilitating meta-metallation with the use of bulky LiCKOR. While the inverted NMe2 group completely suppresses ortho-metallation, the less bulky and more electron withdrawing OMe group demonstrates more rotation freedom allowing selective ortho-metallation with smaller reagents such as n-BuLi or tert-BuLi.

AB - The influence of the bulky trimethylsilyl substituent on the selectivity of metallation of dimethylaniline, anisole and 1-dimethylaminonaphthalene is studied. The neighboring SiMe3 group forces dimethylamino and methoxy groups to occupy a conformation with an unshared electron pair turned towards silicon atom. This forced conformation prevents NMe2 and OMe groups from providing the DOM-effect, thus facilitating meta-metallation with the use of bulky LiCKOR. While the inverted NMe2 group completely suppresses ortho-metallation, the less bulky and more electron withdrawing OMe group demonstrates more rotation freedom allowing selective ortho-metallation with smaller reagents such as n-BuLi or tert-BuLi.

KW - Aniline

KW - Lithiation

KW - Silicon

KW - Sterical effect

KW - PROTON SPONGE

KW - METALATION

UR - http://www.scopus.com/inward/record.url?scp=85076007999&partnerID=8YFLogxK

U2 - 10.1016/j.jorganchem.2019.121068

DO - 10.1016/j.jorganchem.2019.121068

M3 - Article

AN - SCOPUS:85076007999

VL - 906

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

SN - 0022-328X

M1 - 121068

ER -

ID: 49740558