This is another of those textbook reactions, involving reaction of a carbonyl compound with a phosphonium ylid to form an alkene and a phosphine oxide. The reaction continues to be frequently used, in part because it can be highly stereospecific.
Thus the standard version tends to give Z-alkenes with good specificity, and is thought to proceed via an oxaphosphatane 4-ring intermediate. The reaction and its stereochemistry is sensitive to the reagent (including the nature of the R group), and so one model cannot capture all the aspects of this transform. Here I am starting with the very simple model shown above, where R=H (ωB97XD/6-311G(d,p)/SCRF=tetrahydrofuran). There are four transition states to consider; whether the rate-determining (stereochemical determining) step is TS1 or TS2, and whether the relative orientation of the two (in this example methyl) groups are syn or anti, resulting in E– or Z– alkenes. The most interesting issue would be whether the mechanism can account for why the apparently more sterically hindered route leading to the Z-alkene is often the actual outcome.
Leading to E-alkene | |
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TS1 0.0 kcal/mol | TS2 -3.9 |
Leading to Z-alkene | |
TS1 0.0 kcal/mol | TS2 -2.6 |
Key comments about these results:
E-alkene forming | Z-alkene forming |
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E-alkene forming | Z-alkene forming |
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Much more could be done here, but even a fairly simple model of the Wittig reaction can bring a lot of insight into its unique characteristics.
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Dear Henry,
Thank you very much for posting this information. This is very helpful!
Igor,
This probably needs repeating with R=Ph rather than R=H.