biostudies-literatureIida NJapan Society for the Promotion of Science (JSPS) Grants-in-Aid of Scientific Research (B) ProgramAdvanced Catalytic Transformation (ACT-C) Fund from the Japan Science and Technology (JST) AgencyMEXT: Ministry of Education, Culture, Sports, Science & Technology (Japan) Platform for Drug Discovery, Informatics, and Structural Life ScienceDaiko Foundation698-702https://www.ebi.ac.uk/biostudies/studies/S-EPMC4906510biostudies-literatureUnknown4(6)The pentafluorosulfanyl (SF5) group is more electronegative, lipophilic and sterically bulky relative to the well-explored trifluoromethyl (CF3) group. As such, the SF5 group could offer access to pharmaceuticals, agrochemicals and optoelectronic materials with novel properties. Here, the first synthesis of phthalocyanines (Pcs), a class of compounds used as dyes and with potential as photodynamic therapeutics, with a SF5 group directly attached on their peripheral positions is disclosed. The key for this work is the preparation of a series of SF5-containing phthalonitriles, which was beautifully regio-controlled by a stepwise cyanation via ortho-lithiation/iodination from commercially available pentafluorosulfanyl arenes. The macrocyclization of the SF5-containing phthalonitriles to SF5-substituted Pcs required harsh conditions with the exception of the synthesis of β-SF5-substituted Pc. The regiospecificity of the newly developed SF5-substituted Pcs observed by UV/Vis spectra and fluorescence quantum yields depend on the peripheral positon of the SF5 group.ChemistryOpenSynthesis of Phthalocyanines with a Pentafluorosulfanyl Substituent at Peripheral Positions.PMC490651025288045Iida NMori STanaka KSaito NShibata NTokunaga EfalseSynthesis of Phthalocyanines with a Pentafluorosulfanyl Substituent at Peripheral Positions.The pentafluorosulfanyl (SF5) group is more electronegative, lipophilic and sterically bulky relative to the well-explored trifluoromethyl (CF3) group. As such, the SF5 group could offer access to pharmaceuticals, agrochemicals and optoelectronic materials with novel properties. Here, the first synthesis of phthalocyanines (Pcs), a class of compounds used as dyes and with potential as photodynamic therapeutics, with a SF5 group directly attached on their peripheral positions is disclosed. The key for this work is the preparation of a series of SF5-containing phthalonitriles, which was beautifully regio-controlled by a stepwise cyanation via ortho-lithiation/iodination from commercially available pentafluorosulfanyl arenes. The macrocyclization of the SF5-containing phthalonitriles to SF5-substituted Pcs required harsh conditions with the exception of the synthesis of β-SF5-substituted Pc. The regiospecificity of the newly developed SF5-substituted Pcs observed by UV/Vis spectra and fluorescence quantum yields depend on the peripheral positon of the SF5 group.2015-01-01T00:00:00Z2015 Dec2024-10-18T23:55:39.169Z2019-03-27T02:15:59ZS-EPMC49065102730819410.1002/open.201500165