Brown selectivity disobedience of hyperdeaminative Friedel-Crafts benzylation: Electrophilic aromatic substitutions via hyperdeaminatively generated benzyl carbocations

R. W. Darbeau; L. M. Siso; G. A. Trahan; R. S. Nolan

doi:10.2174/1570178053202928

Brown selectivity disobedience of hyperdeaminative Friedel-Crafts benzylation: Electrophilic aromatic substitutions via hyperdeaminatively generated benzyl carbocations

R. W. Darbeau
, L. M. Siso
, G. A. Trahan
, R. S. Nolan

Penn State Altoona

Research output: Contribution to journal › Review article › peer-review

Abstract

Hyperdeamination generates multiple spacer-molecule separated ion-pairs containing high-energy, relatively long-lived carbocations showing near specificity for arenes over their nascent counterions. They exhibit low intermolecular selectivity but surprisingly high intramolecular selectivity. Unlike analogous deaminative benzylations, hyperdeaminative benzylations disobey the Brown Selectivity Relationship. A model for EAS reactions with hyperactive electrophiles is proposed.

Original language	English (US)
Pages (from-to)	139-144
Number of pages	6
Journal	Letters in Organic Chemistry
Volume	2
Issue number	2
DOIs	https://doi.org/10.2174/1570178053202928
State	Published - Mar 2005

All Science Journal Classification (ASJC) codes

Biochemistry
Organic Chemistry

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title = "Brown selectivity disobedience of hyperdeaminative Friedel-Crafts benzylation: Electrophilic aromatic substitutions via hyperdeaminatively generated benzyl carbocations",

abstract = "Hyperdeamination generates multiple spacer-molecule separated ion-pairs containing high-energy, relatively long-lived carbocations showing near specificity for arenes over their nascent counterions. They exhibit low intermolecular selectivity but surprisingly high intramolecular selectivity. Unlike analogous deaminative benzylations, hyperdeaminative benzylations disobey the Brown Selectivity Relationship. A model for EAS reactions with hyperactive electrophiles is proposed.",

author = "Darbeau, \{R. W.\} and Siso, \{L. M.\} and Trahan, \{G. A.\} and Nolan, \{R. S.\}",

year = "2005",

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doi = "10.2174/1570178053202928",

language = "English (US)",

volume = "2",

pages = "139--144",

journal = "Letters in Organic Chemistry",

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T1 - Brown selectivity disobedience of hyperdeaminative Friedel-Crafts benzylation

T2 - Electrophilic aromatic substitutions via hyperdeaminatively generated benzyl carbocations

AU - Darbeau, R. W.

AU - Siso, L. M.

AU - Trahan, G. A.

AU - Nolan, R. S.

PY - 2005/3

Y1 - 2005/3

N2 - Hyperdeamination generates multiple spacer-molecule separated ion-pairs containing high-energy, relatively long-lived carbocations showing near specificity for arenes over their nascent counterions. They exhibit low intermolecular selectivity but surprisingly high intramolecular selectivity. Unlike analogous deaminative benzylations, hyperdeaminative benzylations disobey the Brown Selectivity Relationship. A model for EAS reactions with hyperactive electrophiles is proposed.

AB - Hyperdeamination generates multiple spacer-molecule separated ion-pairs containing high-energy, relatively long-lived carbocations showing near specificity for arenes over their nascent counterions. They exhibit low intermolecular selectivity but surprisingly high intramolecular selectivity. Unlike analogous deaminative benzylations, hyperdeaminative benzylations disobey the Brown Selectivity Relationship. A model for EAS reactions with hyperactive electrophiles is proposed.

UR - https://www.scopus.com/pages/publications/46149108146

UR - https://www.scopus.com/pages/publications/46149108146#tab=citedBy

U2 - 10.2174/1570178053202928

DO - 10.2174/1570178053202928

M3 - Review article

AN - SCOPUS:46149108146

SN - 1570-1786

VL - 2

SP - 139

EP - 144

JO - Letters in Organic Chemistry

JF - Letters in Organic Chemistry

IS - 2

ER -

Brown selectivity disobedience of hyperdeaminative Friedel-Crafts benzylation: Electrophilic aromatic substitutions via hyperdeaminatively generated benzyl carbocations

Abstract

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