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Introduction to the Wittig Reaction and Discussion of the Mechanism

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Investigation of Reactions Involving Pentacoordinate Intermediates

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Abstract

The Wittig reaction [1] is perhaps the most commonly used method for the synthesis of alkenes. Several excellent reviews on the topic have previously been written [2–5]. The reaction (see Scheme 1.1) occurs between a carbonyl compound (aldehyde or ketone in general, 2) and a phosphonium ylide (1). The latter species is a carbanion stabilised by an adjacent phosphorus substituted with three carbons, giving alkene (3) and phosphine oxide (4) as the by-product. The ylide can be represented by resonance structures 1a (fully ionic ylide form) and 1b (ylene form), which show between them the ionic character of the P–C bond and the contribution to the stabilisation of the carbanion by phosphorus.

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Notes

  1. 1.

    See Ref. [3], Chap. 8, pp. 221–273.

  2. 2.

    For details on the SCOOPY-modification of the Wittig reaction, see Ref. [3], Chap. 8, pp. 241, 242.

  3. 3.

    This, somewhat bizarrely given the experimental evidence now available, has recently been suggested by a computational paper to be the only intermediate in the reaction of methylidenetrimethylphosphorane and ethanal in DMSO [62].

  4. 4.

    See, for example, Ref. [67], and also Sect. 1.4.3 later, in which the evidence for the currently accepted mechanism is presented.

  5. 5.

    See Ref. [4], p. 24, Table 6.

  6. 6.

    In crossover experiments for Wittig reactions, a more reactive ylide or aldehyde is added to the reaction mixture after the intermediate has formed but not completely decomposed in order to “mop up” any starting material that re-forms by Wittig reversal.

  7. 7.

    The β-HPSs in this case were actually obtained by a route involving nucleophilic ring opening of an epoxide. Phosphide cleavage of an epoxide of defined stereochemistry, addition of acid to give β-hydroxyphosphine and quaternisation of phosphorus with methyl iodide or triflate gives β-HPS.

  8. 8.

    See Ref. [3] pp. 290, 291.

  9. 9.

    See Ref. [3] pp. 294–296.

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  1. School of Chemistry and Chemical Biology, University College Dublin, Belfield, Dublin, Ireland

    Peter A. Byrne

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Byrne, P.A. (2012). Introduction to the Wittig Reaction and Discussion of the Mechanism. In: Investigation of Reactions Involving Pentacoordinate Intermediates. Springer Theses. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-32045-3_1

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