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. 2011 Dec 30;67(52):100997-10104.
doi: 10.1016/j.tet.2011.09.088. Epub 2011 Sep 24.

Lessons Learned while Traversing the Welwitindolinone Alkaloids Obstacle Course

Vikram Bhat  1 , James A Mackay, Viresh H Rawal
Affiliations

Lessons Learned while Traversing the Welwitindolinone Alkaloids Obstacle Course

Vikram Bhat et al. Tetrahedron. .

Abstract

We recount several unexpected results observed in the course of our work toward the synthesis of welwitindolinone alkaloids. The surprising results provide an opportunity to refine one's understanding of the interplay between chemical structure and reactivity.

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Figures

Figure 1
Figure 1
Representative Welwitindolinone Alkaloids
Figure 2
Figure 2
ORTEP Image of 36
Scheme 1
Scheme 1
Vilsmeier–Haack Deconjugative Methylation Approach
Scheme 2
Scheme 2
Vilsmeier–Haack Chloroformylation of Dione 5
Scheme 3
Scheme 3
Attempts to Functionalize the C12-Position of Dione 5
Scheme 4
Scheme 4
Formation of the Decarboxylated Welwitindolinone
Scheme 5
Scheme 5
Successful Synthesis of the Functionalized Welwitindolinone Core
Scheme 6
Scheme 6
Unexpected Rearrangement during Deoxygenative Chlorination
Scheme 7
Scheme 7
Unanticipated Intramolecular Reaction
Scheme 8
Scheme 8
Attempts to Synthesize the Alkenyl Chloride
Scheme 9
Scheme 9
Plausible Mechanism for the Unusual Rearrangement
See this image and copyright information in PMC

References

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    1. Total syntheses of welwitindolinone A: Baran PS, Richter JM. J Am Chem Soc. 2005;127:15394–15396.Reisman SE, Ready JM, Hasuoka A, Smith CJ, Wood JL. J Am Chem Soc. 2006;128:1448–1449.For the synthesis of welwitindolinone D (3), see ref . (d) While the present manuscript was under review for publication, a report appeared in J. Am. Chem. Soc., ASAP on the total synthesis of welwitindolinone C (2): Huters AD, Quasdorf KW, Styduhar ED, Garg NK. J Am Chem Soc. 2011 doi: 10.1021/ja206538k.

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