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. 2011 Sep 28;133(38):14892-5.
doi: 10.1021/ja2059704. Epub 2011 Sep 1.

Molecular complexity via C-H activation: a dehydrogenative Diels-Alder reaction

Erik M Stang  1 , M Christina White
Affiliations

Molecular complexity via C-H activation: a dehydrogenative Diels-Alder reaction

Erik M Stang et al. J Am Chem Soc. .

Abstract

Traditionally, C-H oxidation reactions install oxidized functionality onto a preformed molecular skeleton, resulting in a local molecular change. The use of C-H activation chemistry to construct complex molecular scaffolds is a new area with tremendous potential in synthesis. We report a Pd(II)/bis-sulfoxide-catalyzed dehydrogenative Diels-Alder reaction that converts simple terminal olefins into complex cycloadducts in a single operation.

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Figures

Figure 1
Figure 1
a Terminal olefin (1.0 equiv.), maleimide (1.0 equiv.), 2,6Me2BQ (1.0 equiv.), p-NO2BzOH (10mol%), DCE(1M), 45°C, 48h. All isolated yields. b~1.3:1 Diastereomeric ratio of facial selectivity, separated using standard chromatography. Major diastereomer shown.
Figure 2
Figure 2
a) Conditions: 2 (10 mol%), NPM (1.0 equiv.), 2,6Me2BQ (1.0 equiv.), p-NO2BzOH (10 mol%), DCE (1M), 45°C, 48 hr. Both cycloadducts were isolated as single diastereomers.
Scheme 1
Scheme 1
a) 2 (10 mol%), 25 (1 equiv.), NPM (1 equiv.), 2,6Me2BQ (1 equiv.), p-NO2BzOH (10 mol%), DCE (1M), 45°C, 73%, >20:1 d.r. b) Zn, AcOH c) PhMe, 80°C, 87% (over 2 steps)
Scheme 2
Scheme 2
a) 2 (10 mol%), 28 (1 equiv.), N-(3,4-dimethoxy)phenethyl maleimide (1 equiv.), 2,6Me2BQ (1 equiv.), p-NO2BzOH (10 mol%), DCE (1M), 45°C, 71%, >20:1 d.r. b) Pd/C (cat.), H2 (1 atm) c) NaBH4, H2SO4 d) CSA, PhMe, 80°C, 71% (over 3 steps), >20:1 d.r.
See this image and copyright information in PMC

References

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