Skip to main content
Chemistry LibreTexts

29.4: Photochemical Electrocyclic Reactions

  • Page ID
    364598
  • \( \newcommand{\vecs}[1]{\overset { \scriptstyle \rightharpoonup} {\mathbf{#1}} } \) \( \newcommand{\vecd}[1]{\overset{-\!-\!\rightharpoonup}{\vphantom{a}\smash {#1}}} \)\(\newcommand{\id}{\mathrm{id}}\) \( \newcommand{\Span}{\mathrm{span}}\) \( \newcommand{\kernel}{\mathrm{null}\,}\) \( \newcommand{\range}{\mathrm{range}\,}\) \( \newcommand{\RealPart}{\mathrm{Re}}\) \( \newcommand{\ImaginaryPart}{\mathrm{Im}}\) \( \newcommand{\Argument}{\mathrm{Arg}}\) \( \newcommand{\norm}[1]{\| #1 \|}\) \( \newcommand{\inner}[2]{\langle #1, #2 \rangle}\) \( \newcommand{\Span}{\mathrm{span}}\) \(\newcommand{\id}{\mathrm{id}}\) \( \newcommand{\Span}{\mathrm{span}}\) \( \newcommand{\kernel}{\mathrm{null}\,}\) \( \newcommand{\range}{\mathrm{range}\,}\) \( \newcommand{\RealPart}{\mathrm{Re}}\) \( \newcommand{\ImaginaryPart}{\mathrm{Im}}\) \( \newcommand{\Argument}{\mathrm{Arg}}\) \( \newcommand{\norm}[1]{\| #1 \|}\) \( \newcommand{\inner}[2]{\langle #1, #2 \rangle}\) \( \newcommand{\Span}{\mathrm{span}}\)\(\newcommand{\AA}{\unicode[.8,0]{x212B}}\)

    As discussed in Section 30.1, irradiation of a conjugated polyene with ultraviolet light causes an electron from the groude-state HOMO to be excited to the ground state LUMO. This creates a new higher energy HOMO in an electron configuration called the excited state. Electron excitation changes the symmetry of the new HOMO which has a corresponding effect on the reaction stereochemistry. Under photochemical reaction conditions conjugated dienes undergo disrotatory cyclization whereas under thermal conditions they underwent conrotatory cyclization. Likewise, conjugated triene undergo conrotatory photochemical cyclization while undergoing disrotatory thermal cyclization. For example, trans,trans-2,4-hexadiene undergoes conrotatory photochemical cyclization to form cis-3,4-dimethylcyclobutene.

    clipboard_e8eb3e99a3d3fec7cdfae528500f34f4c.png Cyclobutene.png

    The conjugated tirene, trans,cis,trans-2,4,6-octatriene undergoes conrotation to form trans-5,6-dimethyl-1,3-cyclohexadiene during photochemical cyclization.

    clipboard_e349dddcb4a18d50c71518282de7d00a6.pngTriene.png

    Generalized Statement of Woodward-Hoffmann Rules for Electrocyclic Reactions

    Thermal and photochemical electrocyclic reactions always produce the opposite stereochemistry products due to the difference in symmetries in their HOMO frontier orbitals. This idea can be combined with the trend of even and odd polyenes to provide simple rules to predict the stereochemistry of electrocyclic reactions.

    Number of Double Bonds Thermal Photochemical
    Odd Disrotatory Conrotatory
    Even Conrotatory Disrotatory
    Exercise \(\PageIndex{1}\)

    Would the following electrocyclic reaction be con or disrotatory? Please draw the expected product.

    Example 1 P.png

    Answer

    An even number of double bonds in photochemical conditions predicts a disrotatory reaction.

    Example 1S.png


    29.4: Photochemical Electrocyclic Reactions is shared under a CC BY-SA 4.0 license and was authored, remixed, and/or curated by Steven Farmer & Kevin M. Shea.