Singly and Doubly Neo-Confused Smaragdyrins

Rao, Yutao; Zhou, Wenjing; Xu, Ling; Zhou, Mingbo; Yin, Bangshao; Tanaka, Takayuki; Osuka, Atsuhiro; Song, Jianxin

doi:10.1021/jacs.9b10270

Cited by 27 publications

(19 citation statements)

References 49 publications

(20 reference statements)

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“…To achieve new structures and functions, the synthetic chemistry of expanded porphyrins has undergone drastic changes in the past two decades. − By combining the N-confusion and core expansion approaches, we have been working on a peculiar kind of porphyrinoid in which N-confused pyrroles play a vital role in the thermodynamic stabilization of the core structures by the inward-directed N-confused nitrogen atom . Besides, such analogs enable specific macrocycle transformation to the internally fused or oxo-type analogs (e.g., doubly N-fused pentaphyrin) due to the inherent high HOMO energy level (Figure b).…”

Section: Introductionmentioning

confidence: 99%

Expanded N-Confused Phlorin: A Platform for a Multiply Fused Polycyclic Ring System via Oxidation within the Macrocycle

Shao

et al. 2020

J. Am. Chem. Soc.

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Novel interrupted π-conjugated macrocycles derived from expanded porphyrinoids were synthesized, and their unique reactivity was investigated in this work. The specific porphyrin analogs, so-called phlorins and isoporphyrins, possess a meso-sp3 methylene moiety, showing inner 3NH and 1NH pyrrolic cores, respectively, and extended near-infrared (NIR) absorption. Expanded N-confused pentapyrrolic phlorin analog 1 bears an interrupted cyclic π-conjugated system that is featured by a distinct higher HOMO and a lower LUMO. Oxidation of 1 allowed structural transformations through the expanded isoporphyrin-like species 2. One of the representative products is a spiro-carbon-bridged multiply N-fused product 3 comprising a fused [5.6.5.7.6.5]-hexacyclic ring obtained by oxidation with 2,3-dichloro-5,6-dicyano-p-benzoquinone. When magic blue was used as the oxidant, an aromatic N-confused pentaphyrin 4 was obtained via migration of one of the meso-phenyl groups to the β-position of the neighboring pyrrolic ring. By employing the flexible cavity of 1 for metal coordination, Pd(II) complexation occurred with a specific meso oxygenation to give a bimetallic complex 5. In contrast to the rich oxidation reactions, reduction of 1 with NaBH4 resulted in the regioselective nucleophilic hydrogen substitution reaction at the para position of one of the meso-C6F5 groups. These results provide a practical approach for synthesizing novel interrupted or aromatic π-conjugated frameworks showing NIR absorptions.

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Section: Introductionmentioning

confidence: 99%

Expanded N-Confused Phlorin: A Platform for a Multiply Fused Polycyclic Ring System via Oxidation within the Macrocycle

Shao

et al. 2020

J. Am. Chem. Soc.

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“…We found that 2 ‐fold S N Ar reaction of 3,5‐dibromo‐8‐mesityl BODIPY 1 with 5,15‐diaryltripyrrane 2 gave [22]smaragdyrin BF 2 complex 3 smoothly (Scheme 1). [4a] We also found that the use of N ‐confused 5,15‐diryltripyrrane 4 led to the formation of Neo‐confused smaragdyrin BF 2 complex 5 , [4b] a new member of neo‐porphyrinoids [5c] (Scheme 1).…”

Section: Methodsmentioning

confidence: 90%

Meso‐Monoaryl‐Substituted Neo‐confused Calixsmaragdyrins and Meso‐monoaryl Substituted Smaragdyrins: Synthesis, Structures and Properties

et al. 2022

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“…Vork urzem berichteten Song und Mitarbeiter über einfach und zweifach neo-invertierte Smaragdyrine. [81]…”

Section: Methodsunclassified

Expandierte Carbaporphyrinoide

Szyszko¹,

Latos‐Grażyński²

2020

Angewandte Chemie

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In diesem Aufsatz sollen die Fortschritte auf dem Gebiet der synthetischen expandierten Carbaporphyrinoide dargelegt werden. Die Entwicklung auf diesem Gebiet wird anhand von expandierten Porphyrin‐verwandten Systemen aufgezeigt, die eine Vielfalt von Bausteinen enthalten, mit deren Hilfe ein oder mehrere Kohlenstoffatome in die Kavität eingeführt werden. Die Ausführungen beginnen mit den Platyrinen – den Makrocyclen, die als Stammmolekül nicht nur der expandierten Carbaporphyrinoide, sondern der Klasse der Carbaporphyrinoide im Allgemeinen gelten. Nach einigen historischen Betrachtungen wird eine Vielzahl von expandierten porphyrinartigen Makrocyclen, die N‐fehlgeordnete oder neo‐fehlgeordnete Pyrrol‐Strukturelemente und verschiedene carbocyclische Untereinheiten enthalten, vorgestellt. Ein besonderer Schwerpunkt wird dabei auf die Anwendungen von expandierten Carbaporphyrinoiden in verschiedenen Bereichen gelegt, z. B. in der Organometallchemie, bei Schaltersystemen oder der Aromatizität. Abschließend wird ein kovalenter Käfig auf der Basis von expandierten Carbaporphyrinoiden vorgestellt.

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Singly and Doubly Neo-Confused Smaragdyrins

Cited by 27 publications

References 49 publications

Expanded N-Confused Phlorin: A Platform for a Multiply Fused Polycyclic Ring System via Oxidation within the Macrocycle

Expanded N-Confused Phlorin: A Platform for a Multiply Fused Polycyclic Ring System via Oxidation within the Macrocycle

Meso‐Monoaryl‐Substituted Neo‐confused Calixsmaragdyrins and Meso‐monoaryl Substituted Smaragdyrins: Synthesis, Structures and Properties

Expandierte Carbaporphyrinoide

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