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Strategic Synthesis of ‘Picket Fence’ Porphyrins Based on Nonplanar Macrocycles**
- Source :
- European Journal of Organic Chemistry
-
Abstract
- Traditional ‘picket fence’ porphyrin systems have been a topic of interest for their capacity to direct steric shielding effects selectively to one side of the macrocycle. Sterically overcrowded porphyrin systems that adopt macrocycle deformations have recently drawn attention for their applications in organocatalysis and sensing. Here we explore the combined benefits of nonplanar porphyrins and the old molecular design to bring new concepts to the playing field. The challenging ortho‐positions of meso‐phenyl residues in dodecasubstituted porphyrin systems led us to transition to less hindered para‐ and meta‐sites and develop selective demethylation based on the steric interplay. Isolation of the symmetrical target compound [2,3,7,8,12,13,17,18‐octaethyl‐5,10,15,20‐tetrakis(3,5‐dipivaloyloxyphenyl)porphyrin] was investigated under two synthetic pathways. The obtained insight was used to isolate unsymmetrical [2,3,7,8,12,13,17,18‐octaethyl‐5,10,15,20‐tetrakis(2‐nitro‐5‐pivaloyloxyphenyl)porphyrin]. Upon separation of the atropisomers, a detailed single‐crystal X‐ray crystallographic analysis highlighted intrinsic intermolecular interactions. The nonplanarity of these systems in combination with ‘picket fence’ motifs provides an important feature in the design of supramolecular ensembles.<br />Nonplanar picket‐fence porphyrins: Two sterically demanding systems, heavy beta substitution and pivalate groups, meet as an intrinsic supramolecular design on a porphyrin scaffold. The symmetrical, double‐sided, and unsymmetrical porphyrins were synthesized and analyzed by X‐ray crystallography, highlighting the combined benefits of steric interplay in designing supramolecular ensembles.
- Subjects :
- Steric effects
Curved π-systems
Atropisomer
Full Paper
010405 organic chemistry
Organic Chemistry
Intermolecular force
Supramolecular chemistry
Porphyrinoids
Atropisomers
Full Papers
010402 general chemistry
01 natural sciences
Porphyrin
Combinatorial chemistry
Supramolecular Chemistry
ddc
0104 chemical sciences
chemistry.chemical_compound
chemistry
Organocatalysis
Via fence
Physical and Theoretical Chemistry
Macrocycles
Subjects
Details
- Language :
- English
- ISSN :
- 10990690 and 1434193X
- Volume :
- 2021
- Issue :
- 12
- Database :
- OpenAIRE
- Journal :
- European Journal of Organic Chemistry
- Accession number :
- edsair.doi.dedup.....59ed903f9ef72fa76bf386a365e80fd9
- Full Text :
- https://doi.org/10.1002/ejoc.202100154