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.
| Language | English |
|---|---|
| Pages | 834-837 |
| Number of pages | 4 |
| Journal | Science |
| Volume | 346 |
| Issue number | 6211 |
| DOIs | |
| Publication status | Published - 14 Nov 2014 |
Fingerprint
Keywords
- benzene
- organometallic compound
- reaction kinetics
Cite this
}
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 journal › Article
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 -