Tetrapyrrole products from electrochemical cyclization of 1′,8′-Disubstituted-a,c-biladiene salts

Swanson, K.L.; Snow, Kevin M.; Jeyakumar, D.; Smith, Kevin M.

doi:10.1016/s0040-4020(01)87058-7

Cited by 22 publications

(8 citation statements)

References 16 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The mechanism of this cyclization, which involves loss of (at least) one of the terminal methyl groups of the a,c-biladiene is not immediately obvious, and a full review of the evidence and conclusions has been published [56]. A breakthrough in the mechanistic investigation of a,c-biladiene cyclizations was achieved when it was shown [56, 60, 61] that electrochemical oxidation of, for example, a,c-biladiene dihydrobromide 68 proceeds to give metal free porphyrin 69 via the cyclic dihydroporphyrin intermediate 70 (Scheme 19 ) which then eliminates the quaternary methyl group (presumably by an S N 2 attack that involves the newly aromatized porphyrin as the leaving group) after macrocyclization.…”

Section: Porphyrin Synthesesmentioning

confidence: 99%

“…The electrochemical cyclization [60, 61] has the advantage that it gives the metal free porphyrin ( e.g. 69 ) as the product, thereby eliminating the need to treat the copper(II) complex [from the copper(II) chloride route] with concentrated sulfuric and trifluoroacetic acids.…”

Section: Porphyrin Synthesesmentioning

confidence: 99%

“…Any other method for cyclization, e.g. the chromium(III) method [54, 66], or electrochemical methods [60, 61] which give directly the metal free porphyrin can be used.…”

Section: Porphyrin Synthesesmentioning

confidence: 99%

See 2 more Smart Citations

Syntheses and Functionalizations of Porphyrin Macrocycles

Vicente¹,

Smith²

2014

COS

110

View full text Add to dashboard Cite

Porphyrin macrocycles have been the subject of intense study in the last century because they are widely distributed in nature, usually as metal complexes of either iron or magnesium. As such, they serve as the prosthetic groups in a wide variety of primary metabolites, such as hemoglobins, myoglobins, cytochromes, catalases, peroxidases, chlorophylls, and bacteriochlorophylls; these compounds have multiple applications in materials science, biology and medicine. This article describes current methodology for preparation of simple, symmetrical model porphyrins, as well as more complex protocols for preparation of unsymmetrically substituted porphyrin macrocycles similar to those found in nature. The basic chemical reactivity of porphyrins and metalloporphyrin is also described, including electrophilic and nucleophilic reactions, oxidations, reductions, and metal-mediated cross-coupling reactions. Using the synthetic approaches and reactivity profiles presented, eventually almost any substituted porphyrin system can be prepared for applications in a variety of areas, including in catalysis, electron transport, model biological systems and therapeutics.

show abstract

Section: Porphyrin Synthesesmentioning

confidence: 99%

Section: Porphyrin Synthesesmentioning

confidence: 99%

See 1 more Smart Citation

Syntheses and Functionalizations of Porphyrin Macrocycles

Vicente¹,

Smith²

2014

COS

110

View full text Add to dashboard Cite

show abstract

“…Homoporphyrins can also be made by treating zinc tetraphenylporphyrin with disubstituted diazoalkanes 11e and by reacting a 1,19-disubstituted biladiene- a , c with cuprous ion in DMF followed by an acid catalyzed rearrangement to the homoporphyrin or by direct electrochemical oxidation of the biladiene- a , c . A homoazaporphyrin ( 8 ) has been reported from the reaction of octaethylporphyrin with N -(ethoxycarbonyl)- p -nitrobenzenesulfonamide …”

Section: Homoporphyrinsmentioning

confidence: 99%

Expanded Porphyrins and Their Heterologs

1997

View full text Add to dashboard Cite

“…Cyclization of 40 then proceeds as reported earlier. Numerous alternative methods for oxidative cyclization of 1,19-dimethyl-a,c-biladiene salts [50,52,53,56,57], including anodic oxidation [58,59], have been reported.…”

Section: By Using 119-dimethyl-ac-biladienesmentioning

confidence: 99%

Syntheses and chemistry of porphyrins

SMITH

2000

J. Porphyrins Phthalocyanines

Self Cite

View full text Add to dashboard Cite

Common methods available for the preparation of useful porphyrins from naturally derived heme and by total synthesis from monopyrroles are presented. Such porphyrins can be used for numerous reactivity and structural modification studies of the type which will be presented in minisymposia (including that entitled ‘Syntheses and Chemistry of Porphyrins’) at the First International Conference on Porphyrins and Phthalocyanines (ICPP-1).

show abstract

Tetrapyrrole products from electrochemical cyclization of 1′,8′-Disubstituted-a,c-biladiene salts

Cited by 22 publications

References 16 publications

Syntheses and Functionalizations of Porphyrin Macrocycles

Syntheses and Functionalizations of Porphyrin Macrocycles

Expanded Porphyrins and Their Heterologs

Syntheses and chemistry of porphyrins

Contact Info

Product

Resources

About