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. 2014 Apr 1;70(17):2738-2745.
doi: 10.1016/j.tet.2014.02.091.

Formyl Group Activation of a Bromopyrrole Ester in Suzuki Cross-Coupling Reactions: Application to a Formal Synthesis of Polycitone A and B and Polycitrin A

John T Gupton  1 , Nakul Telang  1 , Michael Wormald  1 , Kristin Lescalleet  1 , Jon Patteson  1 , Will Curry  1 , Andrew Harrison  1 , Megan Hoerrner  1 , John Sobieski  1 , Michael Kimmel  1 , Emily Kluball  1 , Thomas Perry  1
Affiliations

Formyl Group Activation of a Bromopyrrole Ester in Suzuki Cross-Coupling Reactions: Application to a Formal Synthesis of Polycitone A and B and Polycitrin A

John T Gupton et al. Tetrahedron. .

Abstract

A new pyrrole building block is described, which allows for the regiospecific synthesis of 2,3,5-trisubstituted pyrroles and 2,3,4,5- tetrasubstituted pyrroles. Optimization studies are presented for the preparation of the pyrrole building block along with the evaluation of various cross-coupling conditions and cross-coupling agents. A short, formal synthesis of the natural products Polycitone A, Polycitone B and Polycitrin A from the pyrrole building block is also described.

Keywords: Marine Natural Products; Pyrrole; Suzuki Cross-Coupling; Vilsmeier Formylation.

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Figures

Figure 1
Figure 1
Polycitone A (1a) and Polycitone B (1b) and Polycitrin A (2)
Scheme 1
Scheme 1
Gupton Group Synthesis of Key Polycitone Precursor
Scheme 2
Scheme 2
Formylation of Ethyl 4-Bromopyrrole-2-carboxylate
Scheme 3
Scheme 3
Suzuki Cross-coupling Studies of Ethyl 3-Bromo-2-formylpyrrole-5-carboxylate with Potassium 4-Methylphenyltrifluoroborate
Scheme 4
Scheme 4
Optimization of the Stoichiometry for the Suzuki-Cross-coupling Reaction of Ethyl 3-Bromo-2-formylpyrrole-5-carboxylate with Potassium 4-Methylphenyltrifluoroborate
Scheme 5
Scheme 5
Suzuki Cross-coupling Reactions of Ethyl 3-Bromo-2- formylpyrrole-5-carboxylate with Various Aryl and Heteroarylboronic Acid Derivatives
Scheme 6
Scheme 6
Selective Preparation of Isomeric 3,4-Diarylpyrroles via Formyl Group Activation
Scheme 7
Scheme 7
Formal Synthesis of Polycitone A, Polycitone B and Polycitrin A
See this image and copyright information in PMC

References

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