Palladium-catalyzed Kumada Coupling Reaction of Bromoporphyrins with Silylmethyl Grignard Reagents: Preparation of Silylmethyl-substituted Porphyrins as a Multipurpose Synthon for Fabrication of Porphyrin Systems

Sugita, Noriaki; Hayashi, Satoshi; Hino, Fumio; Takanami, Toshikatsu

doi:10.1021/jo302122f

Cited by 26 publications

(13 citation statements)

References 71 publications

(35 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Silylmethyl-substituted porphyrins, such as 105 , are prepared by palladium(0)-catalyzed Kumada cross-coupling reactions of both meso - and β-bromoporphyrins with silylmethyl Grignard reagents [148]. For example, 105 was obtained from porphyrin 81 in 82% yield (Scheme 37 ).…”

Section: Porphyrin Functionalizationmentioning

confidence: 99%

Syntheses and Functionalizations of Porphyrin Macrocycles

Vicente¹,

Smith²

2014

COS

108

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 Functionalizationmentioning

confidence: 99%

Syntheses and Functionalizations of Porphyrin Macrocycles

Vicente¹,

Smith²

2014

COS

108

View full text Add to dashboard Cite

show abstract

“…As reported by Palomo andc o-workers, [18] the BTSM group can be transformed into am ethyl, formyl, or styryl group. [19] Thus, the dialdehyde 10 a was prepared by oxidation of 9k with ceric ammonium nitrate(CAN;5equiv,258C, 2d)inamixture of acetonitrile and methanol ( Table 3, entry 1). The BTSM group can also undergo aP eterson olefination illustrated by the reaction of (8f)a nd anisaldehyde in the presence of 10 mol %t etra-n-butylammonium fluoride( TBAF) in THF (À20 8C, 15 min) leading to the stilbene derivative 10 b in 92 % yield ( Table 3, entry 2).…”

Section: Resultsmentioning

confidence: 99%

Preparation and Regioselective Magnesiation or Lithiation of Bis(trimethylsilyl)methyl‐Substituted Heteroaryls for the Generation of Highly Functionalized Heterocycles

Klatt

Werner

Maximova

et al. 2015

Chemistry A European J

View full text Add to dashboard Cite

A wide range of bis(trimethylsilyl)methyl (BTSM)- substituted heteroaryl derivatives has been prepared by using Kumada-Corriu or Negishi cross-coupling reactions. The regioselective lithiation or magnesiation of these building blocks bearing a bulky BTSM group by using magnesium or lithium 2,2,6,6-tetramethylpiperidide bases followed by quenching reactions with different electrophiles provides various functionalized N-, O-, or S-heterocycles. Furthermore, the BTSM group can then be converted into formyl, methyl, or styryl groups to give access to a variety of highly functionalized heteroaromatics.

show abstract

“…In 2012, Takanami and co-workers studied the synthesis of substituted meso-(silylmethyl)porphyrins 64 via the Pdcatalyzed cross-coupling of meso-bromoporphyrins 63 with silylmethyl Grignard reagents (Scheme 27). 78 Porphyrins are of great importance, they are widely used in catalysis, molecular recognition, pharmaceuticals, and materials. The prepared meso-(silylmethyl)porphyrins are important synthons for preparing porphyrin derivatives.…”

Section: Scheme 26 Synthesis Of a Haspo Palladium Complexmentioning

confidence: 99%

Transition-Metal-Catalyzed Cross-Coupling Reactions of Grignard Reagents

Juhász¹,

Magyar²,

Hell³

2020

Synthesis

View full text Add to dashboard Cite

Transition-metal-catalyzed cross-coupling of organohalides, ethers, sulfides, amines, and alcohols (and derivatives thereof) with Grignard reagents, known as the Kumada–Tamao–Corriu reaction, can be used to prepare important intermediates in the synthesis of numerous biologically active compounds. The most frequently used transition metals are nickel, palladium, and iron, but there are several examples for cross-coupling reactions catalyzed by copper, cobalt, manganese, chromium, etc. salts and complexes. The aim of this review is to summarize the most important transition-metal-catalyzed cross-coupling reactions realized in the period 2000 to 2020.1 Introduction2 Nickel Catalysis3 Palladium Catalysis4 Iron Catalysis5 Catalysis by Other Transition Metals5.1 Cobalt Catalysis5.2 Copper Catalysis5.3 Manganese Catalysis5.4 Chromium Catalysis6 Conclusion

show abstract

Palladium-catalyzed Kumada Coupling Reaction of Bromoporphyrins with Silylmethyl Grignard Reagents: Preparation of Silylmethyl-substituted Porphyrins as a Multipurpose Synthon for Fabrication of Porphyrin Systems

Cited by 26 publications

References 71 publications

Syntheses and Functionalizations of Porphyrin Macrocycles

Syntheses and Functionalizations of Porphyrin Macrocycles

Preparation and Regioselective Magnesiation or Lithiation of Bis(trimethylsilyl)methyl‐Substituted Heteroaryls for the Generation of Highly Functionalized Heterocycles

Transition-Metal-Catalyzed Cross-Coupling Reactions of Grignard Reagents

Contact Info

Product

Resources

About