Directed ortho-meta'- and meta-meta'-dimetalations: a template base approach to deprotonation

Antonio J. Martínez-Martínez, Alan R Kennedy, Robert E Mulvey, Charles T O'Hara

Research output: Contribution to journalArticle

92 Citations (Scopus)

Abstract

The regioselectivity of deprotonation reactions between arene substrates and basic metalating agents is usually governed by the electronic and/or coordinative characteristics of a directing group attached to the benzene ring. Generally, the reaction takes place in the ortho position, adjacent to the substituent. Here, we introduce a protocol by which the metalating agent, a disodium-monomagnesium alkyl-amide, forms a template that extends regioselectivity to more distant arene sites. Depending on the nature of the directing group, ortho-meta' or meta-meta' dimetalation is observed, in the latter case breaking the dogma of ortho metalation. This concept is elaborated through the characterization of both organometallic intermediates and electrophilically quenched products.

LanguageEnglish
Pages834-837
Number of pages4
JournalScience
Volume346
Issue number6211
DOIs
Publication statusPublished - 14 Nov 2014

Fingerprint

Benzene
Amides

Keywords

  • benzene
  • organometallic compound
  • reaction kinetics

Cite this

@article{6274bb98698f409f9f7c07d4a98c98fd,
title = "Directed ortho-meta'- and meta-meta'-dimetalations: a template base approach to deprotonation",
abstract = "The regioselectivity of deprotonation reactions between arene substrates and basic metalating agents is usually governed by the electronic and/or coordinative characteristics of a directing group attached to the benzene ring. Generally, the reaction takes place in the ortho position, adjacent to the substituent. Here, we introduce a protocol by which the metalating agent, a disodium-monomagnesium alkyl-amide, forms a template that extends regioselectivity to more distant arene sites. Depending on the nature of the directing group, ortho-meta' or meta-meta' dimetalation is observed, in the latter case breaking the dogma of ortho metalation. This concept is elaborated through the characterization of both organometallic intermediates and electrophilically quenched products.",
keywords = "benzene, organometallic compound, reaction kinetics",
author = "Mart{\'i}nez-Mart{\'i}nez, {Antonio J.} and Kennedy, {Alan R} and Mulvey, {Robert E} and O'Hara, {Charles T}",
year = "2014",
month = "11",
day = "14",
doi = "10.1126/science.1259662",
language = "English",
volume = "346",
pages = "834--837",
journal = "Science",
issn = "0036-8075",
number = "6211",

}

Directed ortho-meta'- and meta-meta'-dimetalations : a template base approach to deprotonation. / Martínez-Martínez, Antonio J.; Kennedy, Alan R; Mulvey, Robert E; O'Hara, Charles T.

In: Science, Vol. 346, No. 6211, 14.11.2014, p. 834-837.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Directed ortho-meta'- and meta-meta'-dimetalations

T2 - Science

AU - Martínez-Martínez, Antonio J.

AU - Kennedy, Alan R

AU - Mulvey, Robert E

AU - O'Hara, Charles T

PY - 2014/11/14

Y1 - 2014/11/14

N2 - The regioselectivity of deprotonation reactions between arene substrates and basic metalating agents is usually governed by the electronic and/or coordinative characteristics of a directing group attached to the benzene ring. Generally, the reaction takes place in the ortho position, adjacent to the substituent. Here, we introduce a protocol by which the metalating agent, a disodium-monomagnesium alkyl-amide, forms a template that extends regioselectivity to more distant arene sites. Depending on the nature of the directing group, ortho-meta' or meta-meta' dimetalation is observed, in the latter case breaking the dogma of ortho metalation. This concept is elaborated through the characterization of both organometallic intermediates and electrophilically quenched products.

AB - The regioselectivity of deprotonation reactions between arene substrates and basic metalating agents is usually governed by the electronic and/or coordinative characteristics of a directing group attached to the benzene ring. Generally, the reaction takes place in the ortho position, adjacent to the substituent. Here, we introduce a protocol by which the metalating agent, a disodium-monomagnesium alkyl-amide, forms a template that extends regioselectivity to more distant arene sites. Depending on the nature of the directing group, ortho-meta' or meta-meta' dimetalation is observed, in the latter case breaking the dogma of ortho metalation. This concept is elaborated through the characterization of both organometallic intermediates and electrophilically quenched products.

KW - benzene

KW - organometallic compound

KW - reaction kinetics

UR - http://www.scopus.com/inward/record.url?scp=84910651893&partnerID=8YFLogxK

UR - http://www.sciencemag.org/

U2 - 10.1126/science.1259662

DO - 10.1126/science.1259662

M3 - Article

VL - 346

SP - 834

EP - 837

JO - Science

JF - Science

SN - 0036-8075

IS - 6211

ER -