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Wittig Reactions of Aldehydes Bearing a β-Heteroatom Substituent

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Book cover Investigation of Reactions Involving Pentacoordinate Intermediates

Part of the book series: Springer Theses ((Springer Theses))

Abstract

In this work, the kinetic selectivity of the OPA forming step in Wittig reactions of semi-stabilised and stabilised ylides is inferred from the observed Z/E ratio of the alkene product. It is thus very important to be sure that the alkene Z/E ratio is truly reflective of the kinetic OPA cis/trans ratio, and to be aware of possible means by which there may arise a non-correspondence between the two ratios. Changes may occur to the Z/E ratio both during and after the Wittig reaction. The latter problem is prosaic but pernicious. It is not sufficiently recognised that Z-1,2-disubstituted alkenes are quite easily converted, under a variety of conditions, to a Z/E mixture and sometimes completely to the E-isomer.

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Notes

  1. 1.

    2,2′-difluorostilbene is extremely prone to isomerisation—see Ref. [4].

  2. 2.

    See Ref. [3] pp. 61–70.

  3. 3.

    See Sect. 2.3.2.

  4. 4.

    See Sect. 2.4.

  5. 5.

    See Sect. 2.3.1.

  6. 6.

    See Ref. [3], pp. 61–70.

  7. 7.

    CCDC-883627 contain the X-ray crystallographic data for this compound. This data can be obtained free of charge from The Cambridge Crystallographic Data Centre via http://www.ccdc.cam.ac.uk/data_request/cif. An image of the crystal structure can be found in Sect. 4.7.2.

  8. 8.

    This assignment has been confirmed by X-ray crystallographic analysis, which is yet to be published. See CCDC-883627 for the full crystallographic data.

  9. 9.

    OPA equilibration does occur in reactions of benzaldehydes with non-stabilised ethylides, but only at or above the temperature at which alkene formation occurs. Below this temperature, OPAs are formed under kinetic control.

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  1. School of Chemistry and Chemical Biology, University College Dublin, Belfield, Dublin 4, Ireland

    Peter A. Byrne

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Correspondence to Peter A. Byrne .

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Byrne, P.A. (2012). Wittig Reactions of Aldehydes Bearing a β-Heteroatom Substituent. In: Investigation of Reactions Involving Pentacoordinate Intermediates. Springer Theses. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-32045-3_2

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