Short I⋯O Interactions in the Crystal Structures of Two 2-Iodo-Phenyl Methyl-Amides as Substrates for Radical Translocation Reactions

Ahtsham Ishaq; John M. D. Storey; William T. A. Harrison

doi:10.3390/chemistry5020083

Short I⋯O Interactions in the Crystal Structures of Two 2-Iodo-Phenyl Methyl-Amides as Substrates for Radical Translocation Reactions

Ahtsham Ishaq, John M. D. Storey, William T. A. Harrison^* (Corresponding Author)

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

15 Downloads (Pure)

Abstract

Radical translocation reactions are finding various uses in organic synthesis, in particular the stereospecific formation of complex natural products. In this work, the syntheses and single-crystal structures of two substituted 2-iodo-phenyl methyl-amides are reported, namely cyclo-propane carboxylic acid (2-iodo-phenyl)-methyl-amide, C11H12INO (1), and cyclo-heptane carboxylic acid (2-iodo-phenyl)-methyl-amide, C15H20INO (2). In each case, the methyl-amide group has a syn conformation, and this grouping is perpendicular to the plane of the benzene ring: these solid-state conformations appear to be well setup to allow an intramolecular hydrogen atom transfer to take place as part of a radical translocation reaction. Short intermolecular I⋯O halogen bonds occur in each crystal structure, leading to [010] chains in 1 [I⋯O = 3.012 (2) Å] and isolated dimers in 2 [I⋯O = 3.024 (4) and 3.057 (4) Å]. The intermolecular interactions are further quantified by Hirshfeld surface analyses.

Original language	English
Pages (from-to)	1233–1242
Number of pages	10
Journal	Chemistry
Volume	5
Issue number	2
Early online date	12 May 2023
DOIs	https://doi.org/10.3390/chemistry5020083
Publication status	Published - 12 May 2023

Bibliographical note

Acknowledgments
We thank the EPSRC National Crystallography Service (University of Southampton, England) for the X-ray data collection for 2.
Funding
This research received no external funding.

Keywords

methyl-amides
halogen bonds
conformational analysis

Access to Document

10.3390/chemistry5020083Licence: CC BY

Ishaq_etal_C_ShortI_O_Interactions_VoR
© 2023 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/)
Final published version, 1.75 MBLicence: CC BY

Cite this

@article{1590b95ecf4b434f88c3275f28f6e7e1,

title = "Short I⋯O Interactions in the Crystal Structures of Two 2-Iodo-Phenyl Methyl-Amides as Substrates for Radical Translocation Reactions",

abstract = "Radical translocation reactions are finding various uses in organic synthesis, in particular the stereospecific formation of complex natural products. In this work, the syntheses and single-crystal structures of two substituted 2-iodo-phenyl methyl-amides are reported, namely cyclo-propane carboxylic acid (2-iodo-phenyl)-methyl-amide, C11H12INO (1), and cyclo-heptane carboxylic acid (2-iodo-phenyl)-methyl-amide, C15H20INO (2). In each case, the methyl-amide group has a syn conformation, and this grouping is perpendicular to the plane of the benzene ring: these solid-state conformations appear to be well setup to allow an intramolecular hydrogen atom transfer to take place as part of a radical translocation reaction. Short intermolecular I⋯O halogen bonds occur in each crystal structure, leading to [010] chains in 1 [I⋯O = 3.012 (2) {\AA}] and isolated dimers in 2 [I⋯O = 3.024 (4) and 3.057 (4) {\AA}]. The intermolecular interactions are further quantified by Hirshfeld surface analyses.",

keywords = "methyl-amides, halogen bonds, conformational analysis",

author = "Ahtsham Ishaq and Storey, {John M. D.} and Harrison, {William T. A.}",

note = "Acknowledgments We thank the EPSRC National Crystallography Service (University of Southampton, England) for the X-ray data collection for 2. Funding This research received no external funding. ",

year = "2023",

month = may,

day = "12",

doi = "10.3390/chemistry5020083",

language = "English",

volume = "5",

pages = "1233–1242",

journal = "Chemistry",

issn = "2624-8549",

publisher = "MDPI",

number = "2",

}

TY - JOUR

T1 - Short I⋯O Interactions in the Crystal Structures of Two 2-Iodo-Phenyl Methyl-Amides as Substrates for Radical Translocation Reactions

AU - Ishaq, Ahtsham

AU - Storey, John M. D.

AU - Harrison, William T. A.

N1 - Acknowledgments We thank the EPSRC National Crystallography Service (University of Southampton, England) for the X-ray data collection for 2. Funding This research received no external funding.

PY - 2023/5/12

Y1 - 2023/5/12

N2 - Radical translocation reactions are finding various uses in organic synthesis, in particular the stereospecific formation of complex natural products. In this work, the syntheses and single-crystal structures of two substituted 2-iodo-phenyl methyl-amides are reported, namely cyclo-propane carboxylic acid (2-iodo-phenyl)-methyl-amide, C11H12INO (1), and cyclo-heptane carboxylic acid (2-iodo-phenyl)-methyl-amide, C15H20INO (2). In each case, the methyl-amide group has a syn conformation, and this grouping is perpendicular to the plane of the benzene ring: these solid-state conformations appear to be well setup to allow an intramolecular hydrogen atom transfer to take place as part of a radical translocation reaction. Short intermolecular I⋯O halogen bonds occur in each crystal structure, leading to [010] chains in 1 [I⋯O = 3.012 (2) Å] and isolated dimers in 2 [I⋯O = 3.024 (4) and 3.057 (4) Å]. The intermolecular interactions are further quantified by Hirshfeld surface analyses.

AB - Radical translocation reactions are finding various uses in organic synthesis, in particular the stereospecific formation of complex natural products. In this work, the syntheses and single-crystal structures of two substituted 2-iodo-phenyl methyl-amides are reported, namely cyclo-propane carboxylic acid (2-iodo-phenyl)-methyl-amide, C11H12INO (1), and cyclo-heptane carboxylic acid (2-iodo-phenyl)-methyl-amide, C15H20INO (2). In each case, the methyl-amide group has a syn conformation, and this grouping is perpendicular to the plane of the benzene ring: these solid-state conformations appear to be well setup to allow an intramolecular hydrogen atom transfer to take place as part of a radical translocation reaction. Short intermolecular I⋯O halogen bonds occur in each crystal structure, leading to [010] chains in 1 [I⋯O = 3.012 (2) Å] and isolated dimers in 2 [I⋯O = 3.024 (4) and 3.057 (4) Å]. The intermolecular interactions are further quantified by Hirshfeld surface analyses.

KW - methyl-amides

KW - halogen bonds

KW - conformational analysis

U2 - 10.3390/chemistry5020083

DO - 10.3390/chemistry5020083

M3 - Article

SN - 2624-8549

VL - 5

SP - 1233

EP - 1242

JO - Chemistry

JF - Chemistry

IS - 2

ER -

Short I⋯O Interactions in the Crystal Structures of Two 2-Iodo-Phenyl Methyl-Amides as Substrates for Radical Translocation Reactions

Abstract

Bibliographical note

Keywords

Access to Document

Fingerprint

Cite this