Journal of the American Chemical Society, volume 139, issue 11, pages 3942-3945

Quantifying Possible Routes for SpnF-Catalyzed Formal Diels–Alder Cycloaddition

Medvedev Michael G. ^{1, 2}

Zeifman Alexey A ²

Novikov Fedor ^{2, 3}

Bushmarinov I. S. ¹

Stroganov Oleg V ^{2, 3}

Titov Ilya Yu ^{2, 3}

Chilov Ghermes G ^{2, 3}

Svitanko Igor V ²

Hide authors affiliations Show authors affiliations: 3 affiliations

X-ray Structural Laboratory, A.N. Nesmeyanov Institute of Organoelement Compounds RAS, 119991 Moscow, Russian Federation |

N.D. Zelinsky Institute of Organic Chemistry RAS, 119991 Moscow, Russian Federation |

MolTech Ltd., Leninskie gory, 1/75 A, 119992 Moscow, Russian Federation |

Publication type: Journal Article

Publication date: 2017-03-07

American Chemical Society (ACS)

Journal: Journal of the American Chemical Society

Quartile SCImago

Quartile WOS

Impact factor: 15

ISSN: 00027863, 15205126

DOI: 10.1021/jacs.6b13243

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General Chemistry

Catalysis

Biochemistry

Colloid and Surface Chemistry

Abstract

The Diels-Alder reaction is a cornerstone of modern organic synthesis. Despite this, it remains essentially inaccessible to biosynthetic approaches. Only a few natural enzymes catalyze even a formal [4 + 2] cycloaddition, and it remains uncertain if any of them proceed via the Diels-Alder mechanism. In this study, we focus on the [4 + 2] cycloaddition step in the biosynthesis of spinosyn A, a reaction catalyzed by SpnF enzyme, one of the most promising "true Diels-Alderase" candidates. The four currently proposed mechanisms (including the Diels-Alder one) for this reaction in water (as a first-order approximation of the enzymatic reaction) are evaluated by an exhaustive quantum mechanical search for possible transition states (728 were found in total). We find that the line between the recently proposed bis-pericyclic [J. Am. Chem. Soc. 2016, 138 (11), 3631] and Diels-Alder routes is blurred, and favorable transition states of both types may coexist. Application of the Curtin-Hammett principle, however, reveals that the bis-pericyclic mechanism accounts for ∼83% of the reaction flow in water, while the classical Diels-Alder mechanism contributes only ∼17%. The current findings provide a route for modeling this reaction inside the SpnF active site and inferring the catalytic architecture of possible Diels-Alderases.

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Citations by journals

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ACS Catalysis	ACS Catalysis, 2, 5.26% ACS Catalysis 2 publications, 5.26%
Journal of the American Chemical Society	Journal of the American Chemical Society, 2, 5.26% Journal of the American Chemical Society 2 publications, 5.26%
Proceedings of the National Academy of Sciences of the United States of America	Proceedings of the National Academy of Sciences of the United States of America, 2, 5.26% Proceedings of the National Academy of Sciences of the United States of America 2 publications, 5.26%
Bulletin of the Chemical Society of Japan	Bulletin of the Chemical Society of Japan, 1, 2.63% Bulletin of the Chemical Society of Japan 1 publication, 2.63%
Journal of Natural Medicines	Journal of Natural Medicines, 1, 2.63% Journal of Natural Medicines 1 publication, 2.63%
Nature	Nature, 1, 2.63% Nature 1 publication, 2.63%
Signal Transduction and Targeted Therapy	Signal Transduction and Targeted Therapy, 1, 2.63% Signal Transduction and Targeted Therapy 1 publication, 2.63%
ChemTexts	ChemTexts, 1, 2.63% ChemTexts 1 publication, 2.63%
Russian Chemical Reviews	Russian Chemical Reviews, 1, 2.63% Russian Chemical Reviews 1 publication, 2.63%
Trends in Chemistry	Trends in Chemistry, 1, 2.63% Trends in Chemistry 1 publication, 2.63%
Journal of Chemical Theory and Computation	Journal of Chemical Theory and Computation, 1, 2.63% Journal of Chemical Theory and Computation 1 publication, 2.63%
Acta Pharmaceutica Sinica B	Acta Pharmaceutica Sinica B, 1, 2.63% Acta Pharmaceutica Sinica B 1 publication, 2.63%
Advanced Synthesis and Catalysis	Advanced Synthesis and Catalysis, 1, 2.63% Advanced Synthesis and Catalysis 1 publication, 2.63%
European Journal of Organic Chemistry	European Journal of Organic Chemistry, 1, 2.63% European Journal of Organic Chemistry 1 publication, 2.63%
Israel Journal of Chemistry	Israel Journal of Chemistry, 1, 2.63% Israel Journal of Chemistry 1 publication, 2.63%
ACS Sustainable Chemistry and Engineering	ACS Sustainable Chemistry and Engineering, 1, 2.63% ACS Sustainable Chemistry and Engineering 1 publication, 2.63%
Organic Letters	Organic Letters, 1, 2.63% Organic Letters 1 publication, 2.63%
Accounts of Chemical Research	Accounts of Chemical Research, 1, 2.63% Accounts of Chemical Research 1 publication, 2.63%
Journal of Physical Chemistry Letters	Journal of Physical Chemistry Letters, 1, 2.63% Journal of Physical Chemistry Letters 1 publication, 2.63%
Chemical Reviews	Chemical Reviews, 1, 2.63% Chemical Reviews 1 publication, 2.63%
Science	Science, 1, 2.63% Science 1 publication, 2.63%
Heterocycles	Heterocycles, 1, 2.63% Heterocycles 1 publication, 2.63%
Synlett	Synlett, 1, 2.63% Synlett 1 publication, 2.63%

	1 2 3 4

Citations by publishers

	2 4 6 8 10 12 14
American Chemical Society (ACS)	American Chemical Society (ACS), 14, 36.84% American Chemical Society (ACS) 14 publications, 36.84%
Elsevier	Elsevier, 7, 18.42% Elsevier 7 publications, 18.42%
Wiley	Wiley, 5, 13.16% Wiley 5 publications, 13.16%
Springer Nature	Springer Nature, 4, 10.53% Springer Nature 4 publications, 10.53%
Proceedings of the National Academy of Sciences (PNAS)	Proceedings of the National Academy of Sciences (PNAS), 2, 5.26% Proceedings of the National Academy of Sciences (PNAS) 2 publications, 5.26%
The Chemical Society of Japan	The Chemical Society of Japan, 1, 2.63% The Chemical Society of Japan 1 publication, 2.63%
Autonomous Non-profit Organization Editorial Board of the journal Uspekhi Khimii	Autonomous Non-profit Organization Editorial Board of the journal Uspekhi Khimii, 1, 2.63% Autonomous Non-profit Organization Editorial Board of the journal Uspekhi Khimii 1 publication, 2.63%
American Association for the Advancement of Science (AAAS)	American Association for the Advancement of Science (AAAS), 1, 2.63% American Association for the Advancement of Science (AAAS) 1 publication, 2.63%
The Japan Institute of Heterocyclic Chemistry	The Japan Institute of Heterocyclic Chemistry, 1, 2.63% The Japan Institute of Heterocyclic Chemistry 1 publication, 2.63%
Thieme	Thieme, 1, 2.63% Thieme 1 publication, 2.63%
	2 4 6 8 10 12 14

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Medvedev M. G. et al. Quantifying Possible Routes for SpnF-Catalyzed Formal Diels–Alder Cycloaddition // Journal of the American Chemical Society. 2017. Vol. 139. No. 11. pp. 3942-3945.

GOST all authors (up to 50) Copy

Medvedev M. G., Zeifman A. A., Novikov F., Bushmarinov I. S., Stroganov O. V., Titov I. Yu., Chilov G. G., Svitanko I. V. Quantifying Possible Routes for SpnF-Catalyzed Formal Diels–Alder Cycloaddition // Journal of the American Chemical Society. 2017. Vol. 139. No. 11. pp. 3942-3945.

RIS |

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RIS Copy

TY - JOUR

DO - 10.1021/jacs.6b13243

UR - https://doi.org/10.1021%2Fjacs.6b13243

TI - Quantifying Possible Routes for SpnF-Catalyzed Formal Diels–Alder Cycloaddition

T2 - Journal of the American Chemical Society

AU - Zeifman, Alexey A

AU - Chilov, Ghermes G

AU - Medvedev, Michael G.

AU - Bushmarinov, I. S.

AU - Novikov, Fedor

AU - Stroganov, Oleg V

AU - Titov, Ilya Yu

AU - Svitanko, Igor V

PY - 2017

DA - 2017/03/07 00:00:00

PB - American Chemical Society (ACS)

SP - 3942-3945

IS - 11

VL - 139

SN - 0002-7863

SN - 1520-5126

ER -

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@article{2017_Medvedev,

author = {Alexey A Zeifman and Ghermes G Chilov and Michael G. Medvedev and I. S. Bushmarinov and Fedor Novikov and Oleg V Stroganov and Ilya Yu Titov and Igor V Svitanko},

title = {Quantifying Possible Routes for SpnF-Catalyzed Formal Diels–Alder Cycloaddition},

journal = {Journal of the American Chemical Society},

year = {2017},

volume = {139},

publisher = {American Chemical Society (ACS)},

month = {mar},

url = {https://doi.org/10.1021%2Fjacs.6b13243},

number = {11},

pages = {3942--3945},

doi = {10.1021/jacs.6b13243}

}

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Medvedev, Michael G., et al. “Quantifying Possible Routes for SpnF-Catalyzed Formal Diels–Alder Cycloaddition.” Journal of the American Chemical Society, vol. 139, no. 11, Mar. 2017, pp. 3942-3945. https://doi.org/10.1021%2Fjacs.6b13243.

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American Chemical Society (ACS)

Journal

Journal of the American Chemical Society

Quartile SCImago

Quartile WOS

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00027863 (Print)
15205126 (Electronic)

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Theoretical Chemistry Group of the IOH RAS

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