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Mechanistic studies of 1,3-dipolar cycloadditions of bicyclic thioisomünchnones with alkenes. A computational rationale focused on donor–acceptor interactions

Mechanistic studies of 1,3-dipolar cycloadditions of bicyclic thioisomünchnones with alkenes. A computational rationale focused on donor–acceptor interactions
Mechanistic studies of 1,3-dipolar cycloadditions of bicyclic thioisomünchnones with alkenes. A computational rationale focused on donor–acceptor interactions
This paper describes a mechanistic study, with the interplay of experiment and theory, on the cycloadditions of a bicyclic mesoionic 1,3-dipole versus a series of representative symmetrical (1-phenyl-1H-pyrrole-2,5-dione and dimethyl maleate) and asymmetrical [(E)-(2-nitrovinyl)benzene, acrylonitrile, and but-3-en-2-one] olefinic dipolarophiles. These results allow a comparative analysis with monocyclic dipoles and open further avenues to structurally diversified heteroatom-rich rings. The unichiral version of the bicyclic dipole leads to adducts containing up to five chiral centers, whose formation proceeds with high levels of facial stereoinduction in reactions involving bulky dipolarophiles. The second and largest part of this study provides a theoretical interrogation on the pericyclic mechanism with DFT-methods [M06-2X/6-311++G(d,p)]. In order to get further mechanistic insights, we have also explored charge transfers between reaction partners using NBO analysis, which satisfactorily justifies the stereochemical outcome.
1477-0520
3438-3452
García de la Concepción, Juan
d8ca3ced-6c21-4c16-82e8-9b50611f4dc1
Ávalos, Martín
472f15e9-0c05-4b63-9566-e3d6e6e70329
Cintas, Pedro
29979233-8382-47a8-bde7-1faf4869308c
Jimenez, José L.
c9e89576-0cb3-4e84-a213-fe7617f55521
Light, Mark
cf57314e-6856-491b-a8d2-2dffc452e161
García de la Concepción, Juan
d8ca3ced-6c21-4c16-82e8-9b50611f4dc1
Ávalos, Martín
472f15e9-0c05-4b63-9566-e3d6e6e70329
Cintas, Pedro
29979233-8382-47a8-bde7-1faf4869308c
Jimenez, José L.
c9e89576-0cb3-4e84-a213-fe7617f55521
Light, Mark
cf57314e-6856-491b-a8d2-2dffc452e161

García de la Concepción, Juan, Ávalos, Martín, Cintas, Pedro, Jimenez, José L. and Light, Mark (2018) Mechanistic studies of 1,3-dipolar cycloadditions of bicyclic thioisomünchnones with alkenes. A computational rationale focused on donor–acceptor interactions. Organic & Biomolecular Chemistry, 16 (18), 3438-3452. (doi:10.1039/C8OB00683K).

Record type: Article

Abstract

This paper describes a mechanistic study, with the interplay of experiment and theory, on the cycloadditions of a bicyclic mesoionic 1,3-dipole versus a series of representative symmetrical (1-phenyl-1H-pyrrole-2,5-dione and dimethyl maleate) and asymmetrical [(E)-(2-nitrovinyl)benzene, acrylonitrile, and but-3-en-2-one] olefinic dipolarophiles. These results allow a comparative analysis with monocyclic dipoles and open further avenues to structurally diversified heteroatom-rich rings. The unichiral version of the bicyclic dipole leads to adducts containing up to five chiral centers, whose formation proceeds with high levels of facial stereoinduction in reactions involving bulky dipolarophiles. The second and largest part of this study provides a theoretical interrogation on the pericyclic mechanism with DFT-methods [M06-2X/6-311++G(d,p)]. In order to get further mechanistic insights, we have also explored charge transfers between reaction partners using NBO analysis, which satisfactorily justifies the stereochemical outcome.

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REVISED-Ms-OBC-000683 - Accepted Manuscript
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Accepted/In Press date: 11 April 2018
e-pub ahead of print date: 11 April 2018

Identifiers

Local EPrints ID: 420269
URI: https://eprints.soton.ac.uk/id/eprint/420269
ISSN: 1477-0520
PURE UUID: 7fb0175d-8d20-4295-ab53-24f1447e9a96
ORCID for Mark Light: ORCID iD orcid.org/0000-0002-0585-0843

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Date deposited: 03 May 2018 16:30
Last modified: 12 Apr 2019 04:01

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