Directed Zincation or Magnesiation of 2- and 4-Pyrones and Their Derivatives

Dorothée S. Ziegler; Lydia Klier; Nicolas Müller; Konstantin Karaghiosoff; Paul Knochel

doi:10.1055/s-0037-1610215

Synthesis, Table of Contents

Synthesis 2018; 50(22): 4383-4394
DOI: 10.1055/s-0037-1610215

paper

Directed Zincation or Magnesiation of 2- and 4-Pyrones and Their Derivatives

Dorothée S. Ziegler

Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstrasse 5–13, Haus F, 81377 München, Germany Email: paul.knochel@cup.uni-muenchen.de

,

Lydia Klier

Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstrasse 5–13, Haus F, 81377 München, Germany Email: paul.knochel@cup.uni-muenchen.de

,

Nicolas Müller

Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstrasse 5–13, Haus F, 81377 München, Germany Email: paul.knochel@cup.uni-muenchen.de

,

Konstantin Karaghiosoff

Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstrasse 5–13, Haus F, 81377 München, Germany Email: paul.knochel@cup.uni-muenchen.de

,

Paul Knochel *

Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstrasse 5–13, Haus F, 81377 München, Germany Email: paul.knochel@cup.uni-muenchen.de

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Abstract

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Dedicated to Professor Scott Denmark on the occasion of his 65^th birthday

Abstract

A regioselective magnesiation of the 2-pyrone scaffold was developed. Magnesiation of this heterocycle by using TMPMgCl·LiCl (TMP = 2,2,6,6-tetramethylpiperidyl) followed by trapping reactions with electrophiles such as aldehydes, allylic bromides, acid chlorides, and aryl iodides provided functionalized 2-pyrones. Furthermore, methyl coumalate and 3,5-dibromo-2H-pyran-2-one were zincated by using TMPZnCl·LiCl to afford zincated heterocycles, which reacted with typical electrophiles. A second magnesiation at position C3 of the 2-pyrone scaffold was achieved by using TMPMgCl·LiCl. Also, the zincation of the 4-pyrone scaffold at position C2 is reported, leading to functionalized 4-pyrones.

Key words

pyrone - metalation - magnesium - zinc - heterocycle functionalization

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References

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