TY - JOUR
T1 - Atropisomers of meso Tetra(N-Mesyl Pyrrol-2-yl) Porphyrins: Synthesis, Isolation and Characterization of All-Pyrrolic Porphyrins
AU - Zhu, Leiming
AU - Himmel, Leonard
AU - Merkes, Jean Michél
AU - Kiessling, Fabian
AU - Rueping, Magnus
AU - Banala, Srinivas
N1 - KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: Financial support by the Excellence Initiative of the German federal and state governments through the I3TM Seed Fund Program is acknowledged. The authors thank Prof. M. Albrecht for generous use of spectrometers.
PY - 2020/1/15
Y1 - 2020/1/15
N2 - Atropisomerism has been observed in a variety of biaryl compounds and meso-aryl substituted porphyrins. However, in porphyrins, this phenomenon had been shown only with o-substituted 6-membered aromatic groups at the meso-position. We show herein that a 5-membered heteroaromatic (N-mesyl-pyrrol-2-yl) group at the meso-position leads to atropisomerism. In addition, we report a ‘one-pot’ synthetic route for the synthesis of ‘all-pyrrolic’ porphyrin (APP) with several N-protection groups (Boc, Cbz, Ms and Ts). Among these groups, we found that only the Ms group gave four individually separable atropisomers of meso-tetra(N-Ms-pyrrol-2-yl) porphyrin. Furthermore, the reductive removal of Cbz- was achieved to obtain meso-tetra(pyrrol-2-yl) porphyrin. Thus, our synthetic procedure provides an easy access to a group of APPs and stable atropisomers, which is expected to expand the application of novel APP-based materials.
AB - Atropisomerism has been observed in a variety of biaryl compounds and meso-aryl substituted porphyrins. However, in porphyrins, this phenomenon had been shown only with o-substituted 6-membered aromatic groups at the meso-position. We show herein that a 5-membered heteroaromatic (N-mesyl-pyrrol-2-yl) group at the meso-position leads to atropisomerism. In addition, we report a ‘one-pot’ synthetic route for the synthesis of ‘all-pyrrolic’ porphyrin (APP) with several N-protection groups (Boc, Cbz, Ms and Ts). Among these groups, we found that only the Ms group gave four individually separable atropisomers of meso-tetra(N-Ms-pyrrol-2-yl) porphyrin. Furthermore, the reductive removal of Cbz- was achieved to obtain meso-tetra(pyrrol-2-yl) porphyrin. Thus, our synthetic procedure provides an easy access to a group of APPs and stable atropisomers, which is expected to expand the application of novel APP-based materials.
UR - http://hdl.handle.net/10754/662254
UR - https://onlinelibrary.wiley.com/doi/abs/10.1002/chem.201905637
UR - http://www.scopus.com/inward/record.url?scp=85081259799&partnerID=8YFLogxK
U2 - 10.1002/chem.201905637
DO - 10.1002/chem.201905637
M3 - Article
C2 - 31943372
SN - 0947-6539
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
ER -