Ab initio quantum chemical and ReaxFF-based study of the intramolecular iminium-enamine conversion in a proline-catalyzed reaction

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Résumé

Among all strategies used by organic chemists to control the stereoselectivity of reactions, organocatalysis, which consists in using the chirality of a small organic molecule, is an increasingly popular method. The prolinecatalyzed aldol reaction was one of the first reported cases that demonstrated the power of organocatalysis in the field of asymmetric synthesis. Previous theoretical contributions focused on the reaction mechanism using quantum mechanics (QM) methods. We here present a theoretical study about one specific step of the proline-catalyzed aldol reaction, namely, the conversion of the iminium intermediate into the corresponding enamine. It consists of an intramolecular rearrangement that involves the transfer of a hydrogen atom. First, we investigate this transfer using modern QM models, that is, density functional theory calculations with the M06-2X functional. On the basis of these QM results, we then assess the performance of a reactive force field, ReaxFF, used in combination with molecular dynamics simulations in order to provide a complementary light on this reaction.

langue originaleAnglais
Pages (de - à)1-11
Nombre de pages11
journalTheoretical Chemistry Accounts
Volume131
Numéro de publication8
Les DOIs
étatPublié - 9 août 2012

Empreinte digitale

Quantum theory
Proline
quantum mechanics
Stereoselectivity
Chirality
Density functional theory
Molecular dynamics
Hydrogen
Atoms
Molecules
chirality
field theory (physics)
Computer simulation
hydrogen atoms
molecular dynamics
density functional theory
synthesis
3-hydroxybutanal
molecules
simulation

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title = "Ab initio quantum chemical and ReaxFF-based study of the intramolecular iminium-enamine conversion in a proline-catalyzed reaction",
abstract = "Among all strategies used by organic chemists to control the stereoselectivity of reactions, organocatalysis, which consists in using the chirality of a small organic molecule, is an increasingly popular method. The prolinecatalyzed aldol reaction was one of the first reported cases that demonstrated the power of organocatalysis in the field of asymmetric synthesis. Previous theoretical contributions focused on the reaction mechanism using quantum mechanics (QM) methods. We here present a theoretical study about one specific step of the proline-catalyzed aldol reaction, namely, the conversion of the iminium intermediate into the corresponding enamine. It consists of an intramolecular rearrangement that involves the transfer of a hydrogen atom. First, we investigate this transfer using modern QM models, that is, density functional theory calculations with the M06-2X functional. On the basis of these QM results, we then assess the performance of a reactive force field, ReaxFF, used in combination with molecular dynamics simulations in order to provide a complementary light on this reaction.",
keywords = "DFT, Enamine, Force field development, Iminium, M06-2X, Molecular dynamics simulation, Organocatalysis, Proline catalysis, Reaction pathway, ReaxFF, Solvent effects",
author = "Hubin, {Pierre O.} and Denis Jacquemin and Laurence Leherte and Andr{\'e}, {Jean Marie} and {van Duin}, {Adri C T} and Vercauteren, {Daniel P.}",
year = "2012",
month = "8",
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language = "English",
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journal = "Theoretical Chemistry Accounts: Theory, Computation, and Modeling",
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TY - JOUR

T1 - Ab initio quantum chemical and ReaxFF-based study of the intramolecular iminium-enamine conversion in a proline-catalyzed reaction

AU - Hubin, Pierre O.

AU - Jacquemin, Denis

AU - Leherte, Laurence

AU - André, Jean Marie

AU - van Duin, Adri C T

AU - Vercauteren, Daniel P.

PY - 2012/8/9

Y1 - 2012/8/9

N2 - Among all strategies used by organic chemists to control the stereoselectivity of reactions, organocatalysis, which consists in using the chirality of a small organic molecule, is an increasingly popular method. The prolinecatalyzed aldol reaction was one of the first reported cases that demonstrated the power of organocatalysis in the field of asymmetric synthesis. Previous theoretical contributions focused on the reaction mechanism using quantum mechanics (QM) methods. We here present a theoretical study about one specific step of the proline-catalyzed aldol reaction, namely, the conversion of the iminium intermediate into the corresponding enamine. It consists of an intramolecular rearrangement that involves the transfer of a hydrogen atom. First, we investigate this transfer using modern QM models, that is, density functional theory calculations with the M06-2X functional. On the basis of these QM results, we then assess the performance of a reactive force field, ReaxFF, used in combination with molecular dynamics simulations in order to provide a complementary light on this reaction.

AB - Among all strategies used by organic chemists to control the stereoselectivity of reactions, organocatalysis, which consists in using the chirality of a small organic molecule, is an increasingly popular method. The prolinecatalyzed aldol reaction was one of the first reported cases that demonstrated the power of organocatalysis in the field of asymmetric synthesis. Previous theoretical contributions focused on the reaction mechanism using quantum mechanics (QM) methods. We here present a theoretical study about one specific step of the proline-catalyzed aldol reaction, namely, the conversion of the iminium intermediate into the corresponding enamine. It consists of an intramolecular rearrangement that involves the transfer of a hydrogen atom. First, we investigate this transfer using modern QM models, that is, density functional theory calculations with the M06-2X functional. On the basis of these QM results, we then assess the performance of a reactive force field, ReaxFF, used in combination with molecular dynamics simulations in order to provide a complementary light on this reaction.

KW - DFT

KW - Enamine

KW - Force field development

KW - Iminium

KW - M06-2X

KW - Molecular dynamics simulation

KW - Organocatalysis

KW - Proline catalysis

KW - Reaction pathway

KW - ReaxFF

KW - Solvent effects

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U2 - 10.1007/s00214-012-1261-4

DO - 10.1007/s00214-012-1261-4

M3 - Article

VL - 131

SP - 1

EP - 11

JO - Theoretical Chemistry Accounts: Theory, Computation, and Modeling

JF - Theoretical Chemistry Accounts: Theory, Computation, and Modeling

SN - 1432-881X

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ER -