Mechanism of reduction of alkylmercuric halides by metal hydrides

Whitesides, George M.; Filippo, Joseph San

doi:10.1021/ja00725a039

Cited by 146 publications

(31 citation statements)

References 5 publications

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“…Indeed, when 8 was subjected to the oxymercuration procedure (Hg(OCOCF 3 ) 2 , CH 2 Cl 2 , RT, aqueous KBr work‐up), an extremely clean conversion to the organomercuric bromide 9 was observed. The latter was not purified but immediately subjected to reductive demercuration with tributyltin hydride;24 this lead to tetrahydropyran 10 in 85 % yield and with a high diastereoselectivity (d.r.=93/7) 25. The relative configuration of 10 indicates that the intramolecular oxymercuration involved, as anticipated, an inversion of configuration at the C7 atom 16, 17.…”

Section: Methodsmentioning

confidence: 99%

A Synthetic Approach towards the C1–C9 Subunit of Zincophorin

Cossy¹,

Blanchard²,

Defosseux³

et al. 2002

Angew. Chem.

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Section: Methodsmentioning

confidence: 99%

A Synthetic Approach towards the C1–C9 Subunit of Zincophorin

Cossy¹,

Blanchard²,

Defosseux³

et al. 2002

Angew. Chem.

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“…Buna rağmen benzonorbornil katyon 8 ise kolaylıkla düzenlenebilmektedir [9]. Ayrıca bu özellik ikinci oksidasyonun hangi kademede vuku bulduğuna ilişkin bulgular da verecektir.…”

Section: şEkil 1 Mn(iii)asetat Oksidasyonunun Mekanizmasıunclassified

Mangan(III)asetat Eşliğinde 2-(3-Bromo-1,2,3,4-tetrahidro-1,4-epoksinaftalen-2-il)-3-hidroksi-5,5-dimetilsiklohekze-2-enon’un Sentezi ve Gümüş Tuzları İle Reaksiyonu

Karahan

Karaca

2017

SDÜ Fen Bil Enst Der

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Anahtar Kelimeler Mangan(III)asetat, Dimedon, OksabenzonorbornadienÖzet: Mn(III)asetat eşliğinde dimedonun oksabenzonorbornadiene katılma reaksiyonundaki ara ürün HBr ile yakalandı. Katılma ürünü AgNO3 ve AgClO4 ile asetik asit içerisinde reaksiyona sokuldu. Beklenen dihidrofuran halkası oluşmadı. Bunun yerine dimedondaki α-karbonunun hidroksillendiği bileşik oluştu. Sentezlenen bileşiklerin yapıları 1 H, 13 C ve 2D-NMR teknikleri ile karakterize edildi. Dimedone, OxabenzonorbornadieneAbstract: The addition of dimedone to oxabenzonorbornadiene was performed using Mn(III)acetate in the presence of HBr. The intermediate formed was trapped by bromine. The product was reacted with AgNO3 and AgClO4 in acetic acid. The expected dihydrofuran derivative was not formed. Instead, a hydroxylated dimedone compound on α-carbon was isolated. The structures of the compounds synthesized were characterized by 1 H, 13 C and 2D-NMR spectroscopy.

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“…An ensuing anti -aldol condensation with E -boron enolate of aldehyde 28 [ step-h ] followed by desilylation [ step-i ] gave rise to the oxymercuration precursor 29 17. Subjecting 29 to the oxymercuration conditions [ step-j ] and subsequent tin hydride reduction of the primary organo-mercury intermediate [ step-k ] led to the anticipated tetrahydropyran formation through an initial cyclopropane ring-opening with an inversion of configuration at C7 and a 93:7 diastereomeric ratio [see aldehydes 30 after standard transformations of step-l through p ] 18. This is a very creative construction of the pyranyl moiety while controlling the C7 and C8 relative stereochemistry.…”

Section: Cossy’s Total Synthesismentioning

confidence: 99%

Challenges in the synthesis of a unique mono-carboxylic acid antibiotic, (+)-zincophorin

2009

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Abstract(+)-Zincophorin, also referred to as M144255 or griseochellin, is a polyoxygenated ionophoric antibiotic that was isolated from Streptomyces griseus in 1984. It possesses strong in vivo activity against Gram-positive bacteria and Clostridium coelchii. Its methyl ester was reported in a patent as having strong inhibitory properties against influenza WSN/virus with reduced toxicity for the host cell. Its ability to strongly bind with Zn 2+ , which is also present in its X-ray structure, is the basis for its name. Over the last two decades, (+)-zincophorin h as attracted an impressive array of synthetic efforts including Danishefsky's first total synthesis along with two recent elegant total syntheses reported by Cossy and Miyashita as well as our own formal total synthesis. This Account provides a comparison of the different synthetic efforts on this novel mono-carboxylic acid antibiotic and documents its interesting isolation, structure determination, and biological activities.

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Mechanism of reduction of alkylmercuric halides by metal hydrides

Cited by 146 publications

References 5 publications

A Synthetic Approach towards the C1–C9 Subunit of Zincophorin

A Synthetic Approach towards the C1–C9 Subunit of Zincophorin

Mangan(III)asetat Eşliğinde 2-(3-Bromo-1,2,3,4-tetrahidro-1,4-epoksinaftalen-2-il)-3-hidroksi-5,5-dimetilsiklohekze-2-enon’un Sentezi ve Gümüş Tuzları İle Reaksiyonu

Challenges in the synthesis of a unique mono-carboxylic acid antibiotic, (+)-zincophorin

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