DOI: 10.1002/poc.1535. Synthetic popularity reflects chemical reactivity

Synthetic popularity reflects chemical reactivity

10.1002/poc.1535

Crossref journal-article

Wiley

Journal of Physical Organic Chemistry (311)

Abstract

AbstractLarge and diverse databases of chemical reactions contain statistically significant information about the propensities of molecules to undergo specific chemical transformations. It is shown that this information can be quantified to reflect reaction thermodynamics/kinetics and can be used to construct primitive (yet accurate) reactivity indices from the counts of reported reactions involving molecules/molecular positions of interest. These indices correlate with frontier orbital (FO) populations or Hammettσandρparameters for a range of reactions involving aromatic substrates. These findings suggest that large chemical databases are not only a historical repository of chemical knowledge but also tools with which one can make useful chemical predictions. Copyright © 2009 John Wiley & Sons, Ltd.

Bibliography

Kowalczyk, B., Bishop, K. J. M., Smoukov, S. K., & Grzybowski, B. A. (2009). Synthetic popularity reflects chemical reactivity. Journal of Physical Organic Chemistry, 22(9), 897â902. Portico.

Authors 4

Bartlomiej Kowalczyk (first)
Kyle J. M. Bishop (additional)
Stoyan K. Smoukov (additional)
Bartosz A. Grzybowski (additional)

References 37 Referenced 14

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{'key': 'e_1_2_6_3_2', 'volume-title': 'Molecular Connectivity in Structure Activity Relationships', 'author': 'Kier L. B.', 'year': '1986'} / Molecular Connectivity in Structure Activity Relationships by Kier L. B. (1986)
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{'key': 'e_1_2_6_8_2', 'volume-title': 'Frontier Orbitals and Reaction Paths: Selected Papers of Kenichi Fukui', 'author': 'Fukui K.', 'year': '1998'} / Frontier Orbitals and Reaction Paths: Selected Papers of Kenichi Fukui by Fukui K. (1998)
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{'key': 'e_1_2_6_14_2', 'volume-title': 'Advanced Organic Chemistry', 'author': 'Carey F. A.', 'year': '1993'} / Advanced Organic Chemistry by Carey F. A. (1993)
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10.1021/ja01280a022
Ortho‐ substituents do not follow Hammett's equation because of additional steric effects.
The net electronic effect of substituentXmay be considered as the sum of two distinct effects: induction and resonance. The effect of resonance is greater forparathan formetasubstituents due to better conjugation of electron pairs in theparaposition. In contrast inductive effects which result from the polarization of bonds are stronger formetathan forparasubstituents which are more distant from the reaction site. Consequently the Hammett constantσdepends not only on the particular substituent but also on the substituent's position and is measured separately formetaandparapositions (denoted asσmandσp respectively).
10.1021/cr00002a004
For other X's the reaction counts are below 5.
{'key': 'e_1_2_6_21_2', 'volume-title': 'The Chemistry of Functional Groups', 'author': 'Hegarty A. F.', 'year': '1978'} / The Chemistry of Functional Groups by Hegarty A. F. (1978)
10.1021/cr60165a003
{'key': 'e_1_2_6_23_2', 'first-page': '615', 'volume': '36', 'author': 'Ueno S.', 'year': '1933', 'journal-title': 'J. Soc. Chem. Ind. (Japan)'} / J. Soc. Chem. Ind. (Japan) by Ueno S. (1933)
{'key': 'e_1_2_6_24_2', 'volume-title': 'Azo and Diazo Chemistry – Aliphatic and Aromatic Compounds', 'author': 'Zollinger H.', 'year': '1961'} / Azo and Diazo Chemistry – Aliphatic and Aromatic Compounds by Zollinger H. (1961)
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10.1093/oso/9780198568315.001.0001 / Data Analysis: A Bayesian Tutorial by Sivia D. S. (2006)

Dates

Type	When
Created	16 years, 4 months ago (April 21, 2009, 6:41 a.m.)
Deposited	1 year, 5 months ago (March 12, 2024, 3:49 p.m.)
Indexed	1 year, 5 months ago (March 12, 2024, 4:11 p.m.)
Issued	16 years, 4 months ago (April 21, 2009)
Published	16 years, 4 months ago (April 21, 2009)
Published Online	16 years, 4 months ago (April 21, 2009)
Published Print	15 years, 11 months ago (Sept. 1, 2009)

Funders 0

None

BibTeX

@article{Kowalczyk_2009, title={Synthetic popularity reflects chemical reactivity}, volume={22}, ISSN={1099-1395}, url={http://dx.doi.org/10.1002/poc.1535}, DOI={10.1002/poc.1535}, number={9}, journal={Journal of Physical Organic Chemistry}, publisher={Wiley}, author={Kowalczyk, Bartlomiej and Bishop, Kyle J. M. and Smoukov, Stoyan K. and Grzybowski, Bartosz A.}, year={2009}, month=apr, pages={897–902} }

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