Nucleophilic conjugate addition, consisting of several addition patterns, is an important synthetic methodology in organic synthesis; in this context, examples of 1,3-addition (a-addition) were rare in addition to the well-known 1,4-addition (�-addition). Chemists have been using the concept of �-addition mode to account for the reaction mechanism of phosphines with electron-deficient alkenoates, allenoates and alkynoates. Recently, we report a three-component reaction initiated by nucleophilic attack of phosphines at a(�')-carbon of an enyne A  . Based upon the IUPAC nomenclature, such nucleophilic attack is formally formulated as a 1,6-conjugate addition (d-addition). In this presentation, we will show the elucidation of unique nucleophilic conjugate a-addition reactions of surveyed polyynoates B  with phosphines through analyses of three-component reaction products of polyynoates, phosphines and aldehydes. The structure of isolated products characterized through spectroscopic and single crystal X-ray diffraction analysis led us to uncover the 1,3-addition unambiguously.                                                           

Uncover nucleophilic conjugate 1,3-addition of phosphines to polyynoates

248th National Meeting (2014)

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