Suzuki Porphyrins:  New Synthons for the Fabrication of Porphyrin-Containing Supramolecular Assemblies

Hyslop, Alison G.; Kellett, Matthew A.; Iovine, Peter M.; Therien, Michael J.

doi:10.1021/ja982410h

Cited by 179 publications

(139 citation statements)

References 21 publications

(17 reference statements)

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“…97103 Recently, transition-metal-catalyzed reactions have been often used for this purpose. Representative examples are Sonogashira coupling, 104106 Stille coupling, 107 SuzukiMiyaura coupling, 108,109 and Co(II)-catalyzed alkyne trimerization reactions. 110114 In 2005, we found that iridiumcatalyzed CH activated direct borylation reaction of 5,15-diaryl porphyrins proceeded nicely with high yield and perfect regioselectivity at ¢-positions next to free meso-positions.…”

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confidence: 99%

Subporphyrins: A Legitimate Ring-Contracted Porphyrin with Versatile Electronic and Optical Properties

Osuka

Tsurumaki

Tanaka

2011

Bulletin of the Chemical Society of Japan

119

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After a brief survey of our efforts in the development of novel porphyrinoids that include mesomeso-linked porphyrin arrays, meso-aryl expanded porphyrins, and transition-metal-catalyzed functionalizations of porphyrins, a particular focus in this account is placed on the chemistry of subporphyrins that has been explored in our group. Subporphyrin is a legitimate ring-contracted porphyrin consisting of three pyrrolic subunits domed in a C 3 symmetric bowl shape. While subporphyrins are simple and small macrocycles and possess a key position in porphyrin chemistry, they had been elusive until our first synthesis of tribenzosubporphines in 2006. Shortly after, synthetic protocols of mesoaryl-substituted subporphyrins were developed to produce various subporphyrins with versatile electronic properties that can be widely tuned by meso-aryl substituents. Raney nickel reduction was used to prepare meso-alkyl-substituted subporphyrins from meso-thienyl-substituted subporphyrins. Subchlorins and subbacteriochlorins were prepared respectively by the reduction of subporphyrins with p-tosylhydrazide and Raney nickel. While subporphyrins and subchlorins share conjugated 14³-electronic circuits, subbacteriochlorins have a rare [13]diazaannulene circuit maintained through the lone-pair electrons of the nitrogen atom. The aromaticity decreases in the order of subporphyrin > subchlorin > subbacteriochlorin, as indicated from 1 H-and 11 B NMR spectra and nuclear independent chemical shift (NICS) calculations. Despite these progresses, the chemistry of subporphyrins is still in the infant stage with many untouched aspects and further improvements in synthetic yields are highly desirable for the developments of the chemistry of subporphyrins as well as their applications in diverse fields. A Brief Survey of Our Efforts in the Exploration of Novel PorphyrinoidsIn the last three decades, we have been involved in the exploration of novel porphyrinoids with intriguing structures, electronic and optical properties, and functions. We entered porphyrin chemistry with the aim to synthesize covalently linked organic constructs that can mimic the whole excitation energy transfer and electron transfer events of the photosynthetic reaction centers within a single molecular entity. 13 In the course of these studies, we fortunately encountered new reactions and structures, which drove us to change our research style from a well-designed, goal-orientated path to a flexible discovery-searching strategy to explore novel porphyrinoids. By following the flexible research style, we have explored mesomeso-linked Zn(II) porphyrin arrays, meso-aryl expanded porphyrins, transition-metal-catalyzed porphyrin modifications, and subporphyrins. After a brief survey of the former three topics, a particular focus is placed on the chemistry of subporphyrins that are legitimate ring-contracted porphyrins. As described below, subporphyrins are a new class of functional molecules, particularly in view of their highly tunable electronic and optical properties.

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confidence: 99%

Subporphyrins: A Legitimate Ring-Contracted Porphyrin with Versatile Electronic and Optical Properties

Osuka

Tsurumaki

Tanaka

2011

Bulletin of the Chemical Society of Japan

119

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“…[1] A short outline of the catalytic transformations of porphyrins should start from the application of the reactions of C-C bond formation. Suzuki coupling is well documented since 1994 when this reaction was first applied by Zhou for the exocyclic transformation of the porphyrin core, [2] porphyrin bearing halogen atoms [3] and borylated porphyrins [4] both find their applications in constructing new carbon-carbon bonds. The same is true for Sonogashira reaction which was first applied for the porphyrin modifications also in 1994, [5] and halogen-substituted porphyrins [6] as well as porphyrins with acetylene moieties [7] participate in the coupling.…”

Section: Introductionmentioning

confidence: 99%

“…Pinacol borane and bis(pinacol) borane are the most widely used reagents for this purpose. Therien [22] proposed an earlier described Masuda protocol [23] to be employed in the synthesis of mono-and di-meso-substituted porphyrins from pinacol borane and corresponding zinc (di)bromoporphyrinates using Pd(PPh 3 ) 2 Cl 2 , this approach was further developed by Zhang and Suslik. [24] Pd(dppf) Cl 2 was helpful for the borylation of 2-bromosubstituted porphyrin, [25] and the methodology was spread for the synthesis of tetra-meso-borylated compounds.…”

Section: Introductionmentioning

confidence: 99%

Transition Metal Catalysis in Porphyrin Modifications

Averin¹,

Yakushev²,

Beletskaya³

2016

MHC

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“…Moreover, bromoporphyrin can also be metalated under Masuda conditions for instance, [3] making the porphyrin more nucleophilic, which can then react with a wide range of brominated compounds. [4] Regioselective iridium(I)-catalyzed C-H bond activation allows for the direct β-borylation of the porphyrin ring without the preparation of brominated intermediate, as a required preliminary step for the synthesis of substituted meso-porphyrins. [5] These features are highly relevant for the synthesis of direct carbon-carbon linked multiporphyrinic arrays.…”

Section: Introductionmentioning

confidence: 99%

Syntheses of Bioinspired Trisporphyrin Scaffoldings from Stepwise Suzuki Coupling Strategies

Camus¹,

Harvey²,

Guilard³

2013

MHC

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This review presents the synthetic approach for the design of tris(macrocycles) as bio-inspired models for light harvesting devices in plants andКлючевые слова: Кросс-сочетание Сузуки, светопоглощающие системы, перенос энергии, кофациальные бис(порфирины), порфириновые диады и триады.

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Suzuki Porphyrins: New Synthons for the Fabrication of Porphyrin-Containing Supramolecular Assemblies

Cited by 179 publications

References 21 publications

Subporphyrins: A Legitimate Ring-Contracted Porphyrin with Versatile Electronic and Optical Properties

Subporphyrins: A Legitimate Ring-Contracted Porphyrin with Versatile Electronic and Optical Properties

Transition Metal Catalysis in Porphyrin Modifications

Syntheses of Bioinspired Trisporphyrin Scaffoldings from Stepwise Suzuki Coupling Strategies

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