TY  - JOUR
A1  - Senge, Mathias O.
A1  - Shaker, Yasser M.
A1  - Pintea, Monica
A1  - Ryppa, Claudia
A1  - Hatscher, Sabine S.
A1  - Ryan, Aoife
A1  - Sergeeva, Yulia
T1  - Synthesis of meso-substituted ABCD-Type porphyrins by functionalization reactions
N2  - Considerable progress has been made in recent years in the search for synthetic methods leading to functionalized porphyrins, especially for modification of either the beta- or meso positions. For the latter, total synthesis based on condensation methods or partial synthesis through functionalization of preformed porphyrin have emerged as possible methods. The increasing number of possible technical and medicinal applications for unsymmetrically meso-substituted porphyrins requires straightforward methods for the preparation of the so-called ABCD-porphyrins, i.e., porphyrins with up to four different meso substituents. Here, we describe new strategies for the synthesis of ABCD-type porphyrins based on porphyrin reactions with organolithium reagents and the use of Pd-catalyzed coupling reactions. With the whole repertoire of contemporary functionalization methods, a comprehensive analysis and comparison of the various strategies for A-, AB-, A(2)B-, ABC-, A(2)BC- and ABCD-type porphyrins is given. In addition, we report on the synthesis of new functionalized derivatives for some of these porphyrin classes. In practical terms and taking an applied-science- oriented approach, the synthesis of unsymmetrically meso-substituted porphyrins is best accomplished by a combination of well-developed condensation methods with subsequent functionalization. by organolithium compounds or transition-metal- catalyzed coupling protocols. The methods described are suitable for the preparation of porphyrins for many divergent applications ranging over amphiphilic porphyrins for photodynamic therapy, push-pull systems for optical applications and chiral systems useful in catalysis to donor-acceptor systems suitable for electron-transfer studies.
Y1  - 2010
UR  - http://www3.interscience.wiley.com/cgi-bin/jhome/27380/
U6  - https://doi.org/10.1002/ejoc.200901113
SN  - 1434-193X
ER  - 
TY  - JOUR
A1  - Senge, Mathias O.
A1  - Flanagan, Keith J.
A1  - Ryan, Aoife A.
A1  - Ryppa, Claudia
A1  - Donath, Mandy
A1  - Twamley, Brendan
T1  - Conformational and structural studies of meso monosubstituted metalloporphyrins-Edge-on molecular interactions of porphyrins in crystals
JF  - Tetrahedron
N2  - A series of meso monosubstituted metalloporphyrins were synthesized to assess the structural chemistry of porphyrins with only one substituent. The structures of four nickel(II) and zinc(II) complexes with either alkyl or aryl residues indicate primarily planar macrocycles. This gives rise to a different type of pi-interactions in the crystal and the formation of dimeric, trimeric or tetrameric porphyrin units that function as building blocks for the overall crystal structure. Notably, some structures exhibit a unique edge-on packing of porphyrins, while the molecules of (5-n-butylporphyrinato)nickel(II) forms an unusual bilayer type structure where rows of two porphyrin macrocycles are separated by the alkyl residues arranged in a head-to-head fashion. This adds to the canon of intermolecular porphyrin packing arrangements and is of relevance for the preparation of ordered nanoscopic porphyrin devices. (C) 2015 Elsevier Ltd. All rights reserved.
KW  - Porphyrins
KW  - Conformational analysis
KW  - Tetrapyrroles
KW  - Crystal structure
KW  - Crystal packing
Y1  - 2016
U6  - https://doi.org/10.1016/j.tet.2015.11.008
SN  - 0040-4020
VL  - 72
SP  - 105
EP  - 115
PB  - Elsevier
CY  - Oxford
ER  -