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. 2012 Sep 7;14(17):4354-7.
doi: 10.1021/ol3017963. Epub 2012 Aug 14.

Rapid construction of the aza-propellane core of acutumine via a photochemical [2 + 2] cycloaddition reaction

Raul Navarro  1 , Sarah E Reisman
Affiliations

Rapid construction of the aza-propellane core of acutumine via a photochemical [2 + 2] cycloaddition reaction

Raul Navarro et al. Org Lett. .

Abstract

Synthetic efforts toward the chlorinated aza-propellane alkaloid acutumine (1) are described. The key vicinal quaternary centers were constructed by a photochemical [2 + 2] cycloaddition reaction of a furanyl-tetrahydroindolone. Dihydroxylation of the [2 + 2] product enabled a tandem retro-aldol/intramolecular ketalization reaction, which revealed the aza-propellane core of 1 while generating an unusual, caged, pentacyclic hemiketal product.

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Figures

Scheme 1
Scheme 1
Retrosynthetic analysis of acutumine (1).
Scheme 2
Scheme 2
Diastereoselective 1,2-addition of furanyl Grignard nucleophiles.
Scheme 3
Scheme 3
Preparation of dihydroindolone 6.
Scheme 4
Scheme 4
[2+2] Photocycloaddition of dihydroindolone 6.
Scheme 5
Scheme 5
[2+2] Photocycloaddition of epoxy enone 19.
Scheme 6
Scheme 6
Isolation of ketal rearrangement product 28.
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References

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