Controlling diastereoselectivity in dearomatizing Diels-Alder reactions of nitroarenes with 2-trimethylsilyloxycyclohexadiene
Controlling diastereoselectivity in dearomatizing Diels-Alder reactions of nitroarenes with 2-trimethylsilyloxycyclohexadiene
Dearomative Diels-Alder cycloadditions between nitroarenes and 2-trimethylsilyloxycyclohexadiene are carried out under high pressure at room temperature in the absence of any chemical promoter. Reactions are performed with different arenes, including the highly aromatic naphthalenes and quinolines. They lead to 3D-scaffolds with exquisite exo-diastereoselectivity. The exo approach is characterized by lower distortion of the substrates in a late TS and by more favorable orbital interactions presumably between the nitro group and the dienic part, explaining the stereoselectivity.
DFT calculations, high pressure, nitroarene, silyloxydiene 3, [4+2] cycloaddition
Powderly, Marian
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Roseau, Mélanie
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Frison, Gilles
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Hammami, Rayhane
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Chausset-Boissarie, Laetitia
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Harrowven, David
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Legros, Julien
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Chataigner, Isabelle
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17 June 2024
Powderly, Marian
6425ae48-d9ec-40e8-887e-e74b61137012
Roseau, Mélanie
c7fc7740-8be7-476e-a011-000ab1b83f3e
Frison, Gilles
dbda2c07-c020-467b-badf-e3c80752a27a
Hammami, Rayhane
cce49528-f20d-4daf-9d06-e4856fff96b3
Chausset-Boissarie, Laetitia
b358db89-e680-4959-90a2-c2b85cc2b7ac
Harrowven, David
bddcfab6-dbde-49df-aec2-42abbcf5d10b
Legros, Julien
0ad85dc7-e84f-4c8c-95a4-2aa46fbe89ec
Chataigner, Isabelle
13a550db-1647-4178-8200-f2547b148729
Powderly, Marian, Roseau, Mélanie, Frison, Gilles, Hammami, Rayhane, Chausset-Boissarie, Laetitia, Harrowven, David, Legros, Julien and Chataigner, Isabelle
(2024)
Controlling diastereoselectivity in dearomatizing Diels-Alder reactions of nitroarenes with 2-trimethylsilyloxycyclohexadiene.
Chemistry - A European Journal, 30 (34), [e202303697].
(doi:10.1002/chem.202303697).
Abstract
Dearomative Diels-Alder cycloadditions between nitroarenes and 2-trimethylsilyloxycyclohexadiene are carried out under high pressure at room temperature in the absence of any chemical promoter. Reactions are performed with different arenes, including the highly aromatic naphthalenes and quinolines. They lead to 3D-scaffolds with exquisite exo-diastereoselectivity. The exo approach is characterized by lower distortion of the substrates in a late TS and by more favorable orbital interactions presumably between the nitro group and the dienic part, explaining the stereoselectivity.
Text
Chemistry A European J - 2024 - Powderly - Controlling Diastereoselectivity in Dearomatizing Diels‐Alder Reactions of
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Accepted/In Press date: 15 April 2024
e-pub ahead of print date: 15 April 2024
Published date: 17 June 2024
Keywords:
DFT calculations, high pressure, nitroarene, silyloxydiene 3, [4+2] cycloaddition
Identifiers
Local EPrints ID: 491011
URI: http://eprints.soton.ac.uk/id/eprint/491011
ISSN: 0947-6539
PURE UUID: 22164ed0-ed8f-41cc-92a4-a28f93e81aa1
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Date deposited: 11 Jun 2024 16:37
Last modified: 12 Jul 2024 01:35
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Contributors
Author:
Marian Powderly
Author:
Mélanie Roseau
Author:
Gilles Frison
Author:
Rayhane Hammami
Author:
Laetitia Chausset-Boissarie
Author:
Julien Legros
Author:
Isabelle Chataigner
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