Palladium-Catalyzed Allylic Alkylation of Allyl Dienol Carbonates: 
Reactivity, Regioselectivity, Enantioselectivity, and Synthetic Applications

Stellios Arseniyadis; Jérémy Fournier; Saravanan Thangavelu; Oscar Lozano; Sébastien Prevost; Alexis Archambeau; Candice Menozzi; Janine Cossy

doi:10.1055/s-0033-1338987

Synlett, Table of Contents

Synlett 2013; 24(18): 2350-2364
DOI: 10.1055/s-0033-1338987

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Palladium-Catalyzed Allylic Alkylation of Allyl Dienol Carbonates: Reactivity, Regioselectivity, Enantioselectivity, and Synthetic Applications

Authors

Stellios Arseniyadis*

Laboratoire de Chimie Organique, ESPCI ParisTech, CNRS (UMR 7084), 10 rue Vauquelin, 75231 Paris Cedex 05, France Fax: +33(1)40794662 Email: stellios.arseniyadis@espci.fr Email: janine.cossy@espci.fr
Jérémy Fournier

Laboratoire de Chimie Organique, ESPCI ParisTech, CNRS (UMR 7084), 10 rue Vauquelin, 75231 Paris Cedex 05, France Fax: +33(1)40794662 Email: stellios.arseniyadis@espci.fr Email: janine.cossy@espci.fr
Saravanan Thangavelu

Laboratoire de Chimie Organique, ESPCI ParisTech, CNRS (UMR 7084), 10 rue Vauquelin, 75231 Paris Cedex 05, France Fax: +33(1)40794662 Email: stellios.arseniyadis@espci.fr Email: janine.cossy@espci.fr
Oscar Lozano

Laboratoire de Chimie Organique, ESPCI ParisTech, CNRS (UMR 7084), 10 rue Vauquelin, 75231 Paris Cedex 05, France Fax: +33(1)40794662 Email: stellios.arseniyadis@espci.fr Email: janine.cossy@espci.fr
Sébastien Prevost

Laboratoire de Chimie Organique, ESPCI ParisTech, CNRS (UMR 7084), 10 rue Vauquelin, 75231 Paris Cedex 05, France Fax: +33(1)40794662 Email: stellios.arseniyadis@espci.fr Email: janine.cossy@espci.fr
Alexis Archambeau

Laboratoire de Chimie Organique, ESPCI ParisTech, CNRS (UMR 7084), 10 rue Vauquelin, 75231 Paris Cedex 05, France Fax: +33(1)40794662 Email: stellios.arseniyadis@espci.fr Email: janine.cossy@espci.fr
Candice Menozzi

Laboratoire de Chimie Organique, ESPCI ParisTech, CNRS (UMR 7084), 10 rue Vauquelin, 75231 Paris Cedex 05, France Fax: +33(1)40794662 Email: stellios.arseniyadis@espci.fr Email: janine.cossy@espci.fr
Janine Cossy*

Laboratoire de Chimie Organique, ESPCI ParisTech, CNRS (UMR 7084), 10 rue Vauquelin, 75231 Paris Cedex 05, France Fax: +33(1)40794662 Email: stellios.arseniyadis@espci.fr Email: janine.cossy@espci.fr

Abstract

All articles of this category

Abstract

For the past several years, the group has focused on the development of useful synthetic tools and on executing creative and efficient routes to biologically active natural products. In this context, we recently applied the palladium-catalyzed decarboxylative allylic alkylation reaction to a new class of substrates, namely allyl dienol carbonates. This method allowed a particularly straightforward access to a wide variety of heterocycles, including 2,4-disubstituted-, 2,3,4- and 2,3,5-trisubstituted-, and 2,3,4,5-tetrasubstituted furans and pyrroles, starting from simple and readily available substrates. An asymmetric version of this method was also developed and applied to the synthesis of enantiomerically enriched butenolides and butyrolactones bearing all-carbon α- and β-quaternary stereogenic centers, respectively. This asymmetric transformation was eventually used as a key step in the total synthesis of two natural products: (–)-nephrosteranic acid and (–)-roccellaric acid. This account summarizes the results of our endeavors.

1 Introduction

2 Palladium-Catalyzed Decarboxylative Allylic Alkylation of Allyl Dienol Carbonates

2.1 Synthesis of Polysubstituted Furans

2.2 Synthesis of Polysubstituted Pyrroles

3 Asymmetric Palladium-Catalyzed Decarboxylative Allylic Alkylation of Allyl Dienol Carbonates

3.1 Synthesis of Enantiomerically Enriched Butenolides

3.2 Synthesis of Enantiomerically Enriched Furanones

3.3 Synthesis of Enantiomerically Enriched Butyrolactones

3.4 Total Syntheses of (–)-Nephrosteranic Acid and (–)-Roccellaric Acid

4 Conclusion

Key words

palladium - allylations - alkylations - carbonates - heterocycles - total synthesis - natural products

Full Text

References

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43 The spectroscopic and physical data for 28 and 29 were consistent with those reported in the literature for (–)-nephrosteranic acid and (–)-roccellaric acid, respectively: 28 {[α]_D ²⁰ –13.8 (c 0.5, CHCl₃); lit. [α]_D ²² –27.2 (c 1.45, CHCl₃)}, 29 {[α]_D ²⁰ –14.9 (c 0.45, CHCl₃), lit. [α]_D ²² –27.0 (c 1.73, CHCl₃)}.