Volume 2019, Issue 14 p. 2448-2452

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Incremental Introduction of Organocatalytic Activity into Conformationally Engineered Porphyrins

Marc Kielmann

orcid.org/0000-0001-5665-7456

School of Chemistry, SFI Tetrapyrrole Laboratory, Trinity Biomedical Sciences Institute, Trinity College Dublin, the University of Dublin, 152-160 Pearse Street, Dublin 2, Ireland

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Nitika Grover,

Nitika Grover

orcid.org/0000-0002-2039-1104

School of Chemistry, SFI Tetrapyrrole Laboratory, Trinity Biomedical Sciences Institute, Trinity College Dublin, the University of Dublin, 152-160 Pearse Street, Dublin 2, Ireland

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Werner W. Kalisch,

Werner W. Kalisch

School of Chemistry, SFI Tetrapyrrole Laboratory, Trinity Biomedical Sciences Institute, Trinity College Dublin, the University of Dublin, 152-160 Pearse Street, Dublin 2, Ireland

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Mathias O. Senge,

Corresponding Author

Mathias O. Senge

orcid.org/0000-0002-7467-1654

School of Chemistry, SFI Tetrapyrrole Laboratory, Trinity Biomedical Sciences Institute, Trinity College Dublin, the University of Dublin, 152-160 Pearse Street, Dublin 2, Ireland

E-mail: [email protected]

http://chemistry.tcd.ie/staff/people/mos/Home.html

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Marc Kielmann,

Marc Kielmann

orcid.org/0000-0001-5665-7456

School of Chemistry, SFI Tetrapyrrole Laboratory, Trinity Biomedical Sciences Institute, Trinity College Dublin, the University of Dublin, 152-160 Pearse Street, Dublin 2, Ireland

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Nitika Grover,

Nitika Grover

orcid.org/0000-0002-2039-1104

School of Chemistry, SFI Tetrapyrrole Laboratory, Trinity Biomedical Sciences Institute, Trinity College Dublin, the University of Dublin, 152-160 Pearse Street, Dublin 2, Ireland

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Werner W. Kalisch,

Werner W. Kalisch

School of Chemistry, SFI Tetrapyrrole Laboratory, Trinity Biomedical Sciences Institute, Trinity College Dublin, the University of Dublin, 152-160 Pearse Street, Dublin 2, Ireland

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Mathias O. Senge,

Corresponding Author

Mathias O. Senge

orcid.org/0000-0002-7467-1654

School of Chemistry, SFI Tetrapyrrole Laboratory, Trinity Biomedical Sciences Institute, Trinity College Dublin, the University of Dublin, 152-160 Pearse Street, Dublin 2, Ireland

E-mail: [email protected]

http://chemistry.tcd.ie/staff/people/mos/Home.html

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First published: 16 January 2019

https://doi.org/10.1002/ejoc.201801691

Citations: 19

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Graphical Abstract

To study the correlation of macrocycle nonplanarity and catalytic activity of free base porphyrins in detail, a series of six tetraphenylporphyrins with graded degree of β-ethyl substitution was applied in organocatalyzed reactions. This was aided by DFT calculations in order to explain the distinct relationship between distortion and catalytic competence.

Abstract

To study the correlation of macrocycle nonplanarity and catalytic activity of free base porphyrins in detail, a series of six tetraphenylporphyrins with graded degree of β-ethyl substitution (“H₂Et_xTPPs” 1–6; x = 0, 2, 4, 6, 8) was applied in organocatalyzed reactions. The macrocycles display incrementally increasing nonplanarity due to repulsive peri-interactions. This creates an out-of-plane vector and better accessibility of the core amine and imine groups as the number of alkyl substituents increases. Following such a molecular engineering approach, the inner core system could be used to activate small molecules as a result of significant saddle distortion. The potential organocatalyst “H₂Et_xTPPs” were used in benchmark sulfa-Michael reactions and we found a distinct relationship between nonplanarity and conversion. These observations were attributed to the combined effect of enhanced basicity and increased H-bonding potential that could facilitate bifunctional organocatalysis. Ultimately, density functional theory (DFT) calculations were performed on 1–6 to monitor some electronic properties of the title compounds.

Supporting Information

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Volume2019, Issue14

April 16, 2019

Pages 2448-2452

Incremental Introduction of Organocatalytic Activity into Conformationally Engineered Porphyrins

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Incremental Introduction of Organocatalytic Activity into Conformationally Engineered Porphyrins

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