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For lithium-free Wittig reactions, studies support a concerted formation of the oxaphosphetane without intervention of a betaine. In particular, phosphonium ylides 1 react with carbonyl compounds 2 via a [2+2] cycloaddition that is sometimes described as having [π 2 s + π 2 a] topology to directly form the oxaphosphetanes 4a and 4b.
It is however less reactive than ylides lacking EWGs. For example they usually fail to react with ketones, necessitating the use of the Horner–Wadsworth–Emmons reaction as an alternative. Such stabilized ylides usually give rise to an E-alkene product when they react, rather than the more usual Z-alkene. A "stabilized" Wittig reagent.
Methylenetriphenylphosphorane is an organophosphorus compound with the formula Ph 3 PCH 2. It is the parent member of the phosphorus ylides, popularly known as Wittig reagents. It is a highly polar, highly basic species.
Halonium ylides can be prepared from allyl halides and metal carbenoids. After a [2,3]-rearrangement, a homoallylhalide is obtained. The active form of Tebbe's reagent is often considered a titanium ylide. Like the Wittig reagent, it is able to replace the oxygen atom on carbonyl groups with a methylene group.
In 1958, Leopold Horner published a modified Wittig reaction using phosphonate-stabilized carbanions. [2] [3] William S. Wadsworth and William D. Emmons further defined the reaction. [4] [5] In contrast to phosphonium ylides used in the Wittig reaction, phosphonate-stabilized carbanions are more nucleophilic but less basic. Likewise ...
The Corey–Fuchs reaction is based on a special case of the Wittig reaction, where two equivalents of triphenylphosphine are used with carbon tetrabromide to produce the triphenylphosphine-dibromomethylene ylide. [2] Step 1 of the Corey-Fuchs reaction, generating the active ylide. This ylide undergoes a Wittig reaction when exposed to an aldehyde.
Cp 2 TiCl 2 + 2 CH 3 MgCl → Cp 2 Ti(CH 3) 2 + 2 MgCl 2. This compound is used for the transformation of carbonyl groups to terminal alkenes. It exhibits similar reactivity to the Tebbe reagent and Wittig reaction. Unlike the Wittig reaction, the Petasis reagent can react with a wide range of aldehydes, ketones and esters. [4]
The original publication by Johnson concerned the reaction of 9-dimethylsulfonium fluorenylide with substituted benzaldehyde derivatives. The attempted Wittig-like reaction failed and a benzalfluorene oxide was obtained instead, noting that "reaction between the sulfur ylid and benzaldehydes did not afford benzalfluorenes as had the phosphorus and arsenic ylids."