Carbohydrate-Modified Fused Pyranosylidene Complexes via Radical Addition of Epoxides to Unsaturated Metal Carbenes

Dötz, Karl Heinz; Silva, Edite Gomes da

doi:10.1016/s0040-4020(00)00714-6

Cited by 26 publications

(10 citation statements)

References 28 publications

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“…Among the various synthetic transformations, the use of Fischer carbenes as substrates in metathesis reactions using Grubbs catalysts [7,8] emerged as a very useful way for the obtainment of seven-, eight-and ninemembered heterocyclic rings, particularly in the case of hydrazino carbene complexes. The exploitation of this reactivity allowed us to label a monomer of a peptide nucleic acid (PNA, an interesting analogue of natural nucleic acids) [9] thus opening the way to new transition metal carbene conjugates of PNAs.…”

Section: Introductionmentioning

confidence: 99%

The electrochemical activity of heteroatom-stabilized Fischer-type carbene complexes

Baldoli

Cerea

Falciola

et al. 2005

Journal of Organometallic Chemistry

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Section: Introductionmentioning

confidence: 99%

The electrochemical activity of heteroatom-stabilized Fischer-type carbene complexes

Baldoli

Cerea

Falciola

et al. 2005

Journal of Organometallic Chemistry

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“…The chiral metal-labelled allylglycine PNA monomers 7a,b were synthesised, in which Fischertype carbene functionality was introduced on monomer 3a,b through a cross-metathesis reaction using both Grubbs catalysts 5 and 6 (Scheme 2). We, 24 and other authors, 25 have recently demonstrated the compatibility of Fischer-type carbene complexes with Grubbs catalysts 5 and 6, and studied the ring-closing and cross-metathesis reactions of appropriately designed Fischer-type carbene complexes of chromium.…”

Section: Fischer-type Carbene-conjugated Pnas (Ftc-pnas)mentioning

confidence: 99%

The Metal-Conjugated Peptide Nucleic Acid Challenge

Baldoli¹,

Cerea²,

Giannini³

et al. 2005

Synlett

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This Account describes the advances in the chemistry of metal-conjugated peptide nucleic acids (PNAs) obtained in our laboratories over the last three years. Our interest in bioorganometallic chemistry began several years ago and led to new PNA research, including the design, synthesis and study of the properties of metalconjugated PNAs with the aim of providing new molecules with suitable spectroscopic or electrochemical markers that may be useful in biomedical diagnostics. We describe three classes of metal-conjugated PNA monomers: Fischer-type carbene complexes (FTC), arene chromium tricarbonyl complexes (ACT) and ferrocene (Fc), all of which are inserted on the a-carbon of the glycine unit in order to provide chiral substrates as well as the chemical and spectroscopic properties of the adducts. In addition, we have obtained a lysine-containing PNA 10-mer conjugated to a FTCC, in which the presence of the organometallic unit seems to stabilise the duplex with a complementary DNA strand. Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) studies of monoand tris-Fc labelled tyrosine PNA monomers have shown constantly reversible signals with high currents; the almost tripled current intensity of the tris-Fc monomer allows a detection limit of 10 -8 .

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“…Epoxide‐derived radicals added efficiently to α,β‐unsaturated carbene complexes as reactive radical acceptors (Scheme ) under these conditions 122. Extensions of this concept by using sugar‐derived carbenes as radical acceptors and by adding radicals derived from glycal epoxides to unsaturated carbenes were also investigated 123. The products obtained (Scheme ) should be of interest for the synthesis of biologically active substances.…”

Section: Epoxide Opening By Single Electron Transfer From Metal Comentioning

confidence: 99%

Strained Heterocycles in Radical Chemistry

2003

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Over the last few decades the use of radicals in synthesis has witnessed an explosive growth through introduction of efficient chain and electron-transfer reactions. Strained heterocycles, in particular, have emerged as a highly versatile and readily available class of radical precursors. The generation of carbinyl radicals of heterocycles has resulted in many elegant applications of heteroatom-centered radicals, such as beta fragmentations, cyclizations, and intramolecular hydrogen atom abstractions. Direct electron transfer to strained heterocycles has been realized through the use of arene radical anions. The method combines the virtues of radical and organometallic chemistry to yield useful functionalized organolithium compounds. Epoxides have been opened with high regioselectivity by titanocene(III) reagents in either stoichiometric or catalytic quantities to yield beta-titanoxy radicals. This development has resulted in many new applications in natural product synthesis.

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Carbohydrate-Modified Fused Pyranosylidene Complexes via Radical Addition of Epoxides to Unsaturated Metal Carbenes

Cited by 26 publications

References 28 publications

The electrochemical activity of heteroatom-stabilized Fischer-type carbene complexes

The electrochemical activity of heteroatom-stabilized Fischer-type carbene complexes

The Metal-Conjugated Peptide Nucleic Acid Challenge

Strained Heterocycles in Radical Chemistry

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