Methanesulfonyl azide diazo transfer reaction

Compounds containing a CH2 bonded to two Z groups (as defined on p. 464) can be converted to diazo compounds on treatment with tosyl azide in the presence of a base,164 The use of phase transfer catalysis increases the convenience of the method.165 p-Dodecylbenzenesul-fonyl azide,166 methanesulfonyl azide,167 and p-acetamidobenzenesulfonyl azide168 also give the reaction. The reaction, which is called the diazo transfer reaction, can also be applied to other reactive positions, e.g., the 5 position of cyclopentadiene.169 The mechanism is probably as follows ... 

The diazo transfer reaction with sulfonyl azides has been extensively used for the preparation of diazo compounds with two electron-withdrawing groups (equation 1 ).28 Toluenesulfonyl azide (13a)29 is the standard reagent used, but due to problems of safety and ease of product separation, several alternative reagents have been developed recently. n-DodecylbenzenesuIfonyl azide (13b)30 is very effective for the preparation of crystalline diazo compounds, while p-acetamidobenzenesulfonyl azide (13c)31 or naph-thalenesulfonyl azide (13d)30 are particularly useful with fairly nonpolar compounds. Other useful reagents are methanesulfonyl azide (13e)32 and p-carboxybenzenesulfonyl azide (13f).33... 

Formylation followed by the deformylation diazo transfer reaction of 4-chromanone (65) produces 2-diazochromanone(66) in overall yield of 55-60%.24 Diazo transfer from methanesulfonyl azide to dimethylbenzosuberone (67) is achieved via deformylation.25... 

Reaction with methanesulfonyl azide In a diazo transfer reaction, dimethyl [2- C]malonate reacts with methanesulfonyl azide and triethylamine to give the corresponding dimethyl... 

The HC1 generated in this reaction destroys one equivalent of diazomethane. This can be avoided by including a base, such as triethylamine, to neutralize the acid.74 Cyclic z-diazoketones, which are not available from acyl chlorides, can be prepared by reaction of an enolate equivalent with a sulfonyl azide. This reaction is called diazo transfer 5 Various arenesulfonyl azides76 and methanesulfonyl azide77 are used most frequently. Several types of compounds can act as the carbon nucleophile. These include the anion of the hydroxymethylene derivative of the ketone78 or the dialkylaminomethylene derivative of... 

Intramolecular C—H insertion, on the other hand, is already a practical alternative for the constmction of cyclobutanols, P-lactams - and of cyclopentane-containing targets. With regard to the latter, diazo transfer can be effected on a large scale with the inexpensive methanesulfonyl azide. The rhodium carboxylate catalysts are effective at very low concentration (<1 mol %) and can easily be recovered from the reaction mixture, if desired. ... 

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