Studien zur Synthese der Mitomycine, 5. Ein neuer Weg zu Mitosanen

Flitsch, Wilhelm; Langer, Werner

doi:10.1002/jlac.198819880504

Cited by 10 publications

(2 citation statements)

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“…Methodology described in a previous synthesis of a C9- and C9a-functionalized mitosane was to be used to effect similar functionalization of the protected quinone 330 ; however, cyclization of N -aryl succinimide 329 via Wittig olefination and subsequent Vilsmeier–Haack formylation was the most advanced reaction reported (Scheme ) …”

Section: Mitomycins: Synthetic Studiesmentioning

confidence: 99%

Mitomycinoid Alkaloids: Mechanism of Action, Biosynthesis, Total Syntheses, and Synthetic Approaches

et al. 2013

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Section: Mitomycins: Synthetic Studiesmentioning

confidence: 99%

Mitomycinoid Alkaloids: Mechanism of Action, Biosynthesis, Total Syntheses, and Synthetic Approaches

et al. 2013

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“…It was felt that the formation of the D-ring of these platforms might be accomplished by nucleophilic attack of the “enolate” species at one imide carbonyl. This attractive option was based on reports showing that 2-succinimidylbenzylphosphonium ylides underwent smooth Wittig olefination intramolecularly to give the mitosane and quinocarcin ring systems, respectively. Previous investigations , in isoquinolinone series also validated the practicality of this approach.…”

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A Domino N-Amidoacylation/Aldol-Type Condensation Approach to the Synthesis of the Topo-I Inhibitor Rosettacin and Derivatives

Comesse

Sanselme

et al. 2008

J. Org. Chem.

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The pot, atom, and step-economic synthesis of Rosettacin topo-I poison and its derivatives has been achieved using a novel domino N-amidoacylation/aldol-type condensation, followed by decarboxylation of the ester function. The key domino procedure simply involves mixing HOBt ester as new reagent with lactam and NaH together in THF or THF/ DMF. The reaction seems to be general and led to suitable N-heterocyclic products in moderate to good yields.

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TheVilsmeier Reaction of Fully Conjugated Carbocycles and Heterocycles

Jones

Stanforth

1996

Organic Reactions

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In 1925 Fischer, Müller, and Vilsmeier published a paper describing the reaction between phosphoryl chloride and N ‐methylacetanilide, giving a number of products, including the quinolinium salt and another salt. The probable course of the reaction was given in a paper by Vilsmeier and Haack in 1927, and they made the important discovery that the reagent obtained from N ‐methylformanilide and phosphoryl chloride, represented as a salt, would react with N,N ‐dimethylaniline, giving 4‐ N,N ‐dimethylaminobenzaldehyde. No 2‐substituted products were observed in this reaction. Other N,N ‐dialkylaniline derivatives, including 3, N,N ‐trimethylaniline and 1‐ N,N ‐dimethylaminonaphthalene were also successfully used as substrates to prepare aromatic aldehyde derivatives. The gradual development of the reagent for synthesis was accompanied by interest in the nature of the reagent. It was discovered that other acid chlorides (e.g., thionyl chloride, carbonyl chloride, and oxalyl chloride) could be used in the reaction and that substituted amides other than formamides gave ketones, although in generally poorer yields. Thionyl chloride frequently gives sulfur‐containing products. The most commonly used amide is dimethylformamide (DMF) and there is now a consensus that the reagent formed from DMF and most acid chlorides, other than phosphoryl chloride, can be represented by the structure given in the chapter, and this is illustrated for the reaction between DMF and carbonyl chloride. The salt is a stable compound and is often isolated before being reacted with a substrate. It seems likely that the most commonly used reagent, that made from DMF and phosphoryl chloride, is an equilibrium mixture of iminium salts. Recent unpublished spectroscopic studies have indicated that in DMF solution there is an equilibrium mixture of iminium compounds. One of the electrophilic chloroiminium salts then reacts with a substrate in an electrophilic substitution process yielding an iminium salt, which is usually hydrolyzed to the aromatic aldehyde. Vinylogous chloroiminium salts can be prepared from the corresponding vinylogous formamide derivatives and these yield, after hydrolysis, α,β‐unsaturated products. This particular reaction is generally limited to more reactive substrates. The formation of carbon–carbon bonds to fully conjugated carbocycles and heterocycles is the subject of this chapter; a subsequent chapter considers carbon–carbon bond‐formation reactions in alkenes (including heterosubstituted alkenes such as enamines and enol ethers), alkynes, and activated methyl and methylene compounds (aldehydes, ketones, carboxylic acid derivatives, and nitriles). It is not surprising that the Vilsmeier reaction has been the subject of many review articles of varying scope and length. With so many excellent reviews dealing with the Vilsmeier reaction, its mechanism, and the structure of the various electrophilic reagents, coverage is restricted to important concepts rather than reiterate all the literature material. A brief description of the mechanism and regiochemistry of the Vilsmeier reaction is presented and this is elaborated with appropriate cases that deal with specific compound types.

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Studien zur Synthese der Mitomycine, 5. Ein neuer Weg zu Mitosanen

Abstract: Ausgehend vom Aldehyd 7d wurden die Mitosane 14 mit einer Gesamtausbeute von 12% ( 1 4~) bzw. 10% 114b) erhalten. Die

Cited by 10 publications

References 16 publications

Mitomycinoid Alkaloids: Mechanism of Action, Biosynthesis, Total Syntheses, and Synthetic Approaches

Mitomycinoid Alkaloids: Mechanism of Action, Biosynthesis, Total Syntheses, and Synthetic Approaches

A Domino N-Amidoacylation/Aldol-Type Condensation Approach to the Synthesis of the Topo-I Inhibitor Rosettacin and Derivatives

TheVilsmeier Reaction of Fully Conjugated Carbocycles and Heterocycles

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