Nitronate anion recognition and modulation of ambident reactivity by hydrogen-bonding receptors

Brian R. Linton; M. Scott Goodman; Andrew D. Hamilton

doi:10.1002/1521-3765(20000703)6:13<2449::AID-CHEM2449>3.0.CO;2-9

Nitronate anion recognition and modulation of ambident reactivity by hydrogen-bonding receptors

Brian R. Linton, M. Scott Goodman, Andrew D. Hamilton

Chemistry

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

Abstract

Nitronate anions were shown to form complexes in DMSO with hydrogen-bonding receptors such as 1,3-dimethylthiourea 1 (K_a = 120M^-1) and bicyclic guanidinium2 (K_a = 3200M^-1). A ditopic bis-thiourea exhibited increased association with substrates, that contained either two nitronates (K_a = 7000M^-1) or a combination of nitronate and carboxylate (K_a = 1200M^-1). Complexation of nitronate resulted in a change in the ambident reactivity during alkylation with p-nitrobenzyl bromide. The predominant reaction pathway was shifted from oxygen alkylation to carbon alkylation as receptor binding strength increased. Kinetic analysis indicated an overall inhibition of nitronate reactivity, and this suggests that greater suppression of the oxygen pathway allows carbon alkylation to predominate.

Original language	English (US)
Pages (from-to)	2449-2455
Number of pages	7
Journal	Chemistry - A European Journal
Volume	6
Issue number	13
DOIs	https://doi.org/10.1002/1521-3765(20000703)6:13<2449::AID-CHEM2449>3.0.CO;2-9
State	Published - Jul 3 2000

Keywords

Ambident nucleophiles
Anions
Hydrogen bonds
Molecular recognition
Receptors

ASJC Scopus subject areas

Catalysis
Organic Chemistry

Access to Document

10.1002/1521-3765(20000703)6:13<2449::AID-CHEM2449>3.0.CO;2-9

Cite this

@article{3a16dba9fbfa457c96e9f95958b44245,

title = "Nitronate anion recognition and modulation of ambident reactivity by hydrogen-bonding receptors",

abstract = "Nitronate anions were shown to form complexes in DMSO with hydrogen-bonding receptors such as 1,3-dimethylthiourea 1 (Ka = 120M-1) and bicyclic guanidinium2 (Ka = 3200M-1). A ditopic bis-thiourea exhibited increased association with substrates, that contained either two nitronates (Ka = 7000M-1) or a combination of nitronate and carboxylate (Ka = 1200M-1). Complexation of nitronate resulted in a change in the ambident reactivity during alkylation with p-nitrobenzyl bromide. The predominant reaction pathway was shifted from oxygen alkylation to carbon alkylation as receptor binding strength increased. Kinetic analysis indicated an overall inhibition of nitronate reactivity, and this suggests that greater suppression of the oxygen pathway allows carbon alkylation to predominate.",

keywords = "Ambident nucleophiles, Anions, Hydrogen bonds, Molecular recognition, Receptors",

author = "Linton, {Brian R.} and Goodman, {M. Scott} and Hamilton, {Andrew D.}",

year = "2000",

month = jul,

day = "3",

doi = "10.1002/1521-3765(20000703)6:13<2449::AID-CHEM2449>3.0.CO;2-9",

language = "English (US)",

volume = "6",

pages = "2449--2455",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "Wiley-VCH Verlag",

number = "13",

}

TY - JOUR

T1 - Nitronate anion recognition and modulation of ambident reactivity by hydrogen-bonding receptors

AU - Linton, Brian R.

AU - Goodman, M. Scott

AU - Hamilton, Andrew D.

PY - 2000/7/3

Y1 - 2000/7/3

N2 - Nitronate anions were shown to form complexes in DMSO with hydrogen-bonding receptors such as 1,3-dimethylthiourea 1 (Ka = 120M-1) and bicyclic guanidinium2 (Ka = 3200M-1). A ditopic bis-thiourea exhibited increased association with substrates, that contained either two nitronates (Ka = 7000M-1) or a combination of nitronate and carboxylate (Ka = 1200M-1). Complexation of nitronate resulted in a change in the ambident reactivity during alkylation with p-nitrobenzyl bromide. The predominant reaction pathway was shifted from oxygen alkylation to carbon alkylation as receptor binding strength increased. Kinetic analysis indicated an overall inhibition of nitronate reactivity, and this suggests that greater suppression of the oxygen pathway allows carbon alkylation to predominate.

AB - Nitronate anions were shown to form complexes in DMSO with hydrogen-bonding receptors such as 1,3-dimethylthiourea 1 (Ka = 120M-1) and bicyclic guanidinium2 (Ka = 3200M-1). A ditopic bis-thiourea exhibited increased association with substrates, that contained either two nitronates (Ka = 7000M-1) or a combination of nitronate and carboxylate (Ka = 1200M-1). Complexation of nitronate resulted in a change in the ambident reactivity during alkylation with p-nitrobenzyl bromide. The predominant reaction pathway was shifted from oxygen alkylation to carbon alkylation as receptor binding strength increased. Kinetic analysis indicated an overall inhibition of nitronate reactivity, and this suggests that greater suppression of the oxygen pathway allows carbon alkylation to predominate.

KW - Ambident nucleophiles

KW - Anions

KW - Hydrogen bonds

KW - Molecular recognition

KW - Receptors

UR - http://www.scopus.com/inward/record.url?scp=0034601025&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0034601025&partnerID=8YFLogxK

U2 - 10.1002/1521-3765(20000703)6:13<2449::AID-CHEM2449>3.0.CO;2-9

DO - 10.1002/1521-3765(20000703)6:13<2449::AID-CHEM2449>3.0.CO;2-9

M3 - Article

C2 - 10939746

AN - SCOPUS:0034601025

SN - 0947-6539

VL - 6

SP - 2449

EP - 2455

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 13

ER -

Nitronate anion recognition and modulation of ambident reactivity by hydrogen-bonding receptors

Abstract

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this