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A Simple Route to Prepare Monofunctionalised 21‐Thia‐, 21,23‐Dithia‐, and 21‐Thia‐23‐oxaporphyrins from Unsymmetrical Thiophene Diols and Their Use in the Synthesis of Covalently Linked Unsymmetrical Porphyrin Dimers
Author(s) -
Punidha Sokkalingam,
Agarwal Neeraj,
Ravikanth Mangalampalli
Publication year - 2005
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200400887
Subject(s) - chemistry , thiophene , synthon , porphyrin , pyrrole , aldehyde , diol , medicinal chemistry , covalent bond , aryl , stereochemistry , organic chemistry , catalysis , alkyl
A series of unsymmetrical thiophene diols has been prepared in two steps from thiophene in 16–46 % yields. The unsymmetrical thiophene diols containing functionalised aryl groups were then used as key synthons for the synthesis of a series of monofunctionalised 21‐thia (N 3 S), 21,23‐dithia (N 2 S 2 ) and 21‐thia‐23‐oxaporphyrins (N 2 SO). Condensation of one equivalent of unsymmetrical diol with either two equivalents of aldehyde and three equivalents of pyrrole, one equivalent of symmetrical 16‐thiatripyrrane or one equivalent of symmetrical 16‐oxatripyrrane under standard porphyrin‐forming conditions resulted in monofunctionalised 21‐thia‐, 21,23‐dithia‐ or 21‐thia‐23‐oxaporphyrins in decent yields. This unsymmetrical diol method is simple, versatile and gives an access for the first time to any desired monofunctionalised porphyrins with N 3 S, N 2 S 2 and N 2 SO porphyrin cores. The use of monofunctionalised N 3 S, N 2 S 2 and N 2 SO porphyrins is further demonstrated by synthesising the first examples of three new covalently linked diarylethyne‐bridged unsymmetrical dimers containing two different porphyrin cores such as N 2 S 2 ‐N 4 , N 2 S 2 ‐N 3 S and N 2 S 2 ‐N 2 SO. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)