Synthesis of Chlorinated Arenes and Hetarenes by One-Pot Cyclizations of 1,3-Bis-silyl Enol Ethers

In memory of our colleague and friend Muhammad Zeeshan.

Abstract

This account describes our recent findings and progress in synthesizing chlorinated arenes and hetarenes by one-pot cyclizations of 1,3-bis-silyl enol ether derivatives. These reactions allow for the preparation of highly functionalized products with a high level of regioselectivity. The synthetic routes are cost-effective avoiding additional functionalization steps. The products are difficult to be accessed by other methods. The chlorine atom is of relevance in medicinal and agriculture chemistry. In addition, it allows further functionalizations by transition-metal-catalyzed cross-coupling reactions.

1 Introduction

2 Cyclizations of 2-Chloro-1,3-bis(silyloxy)-1,3-butadienes

2.1 3,5-Dihydroxychlorophthalates

2.2 2,4-Dihydroxy-homochlorophthalates

2.3 2-(Arylsulfonyl)chloropyridines

2.4 1-Azaxanthones

3 Cyclizations of 4-Chloro-1,3-bis(trimethylsilyloxy)-1,3-butadienes

3.1 3-Chlorosalicylates

3.2 Functionalized Chlorobiaryls

3.3 3-Chloro-5-(2-chloroethyl)-salicylates

3.4 2,4-Dihydroxychlorobenzophenones

4 Cyclizations of 2-Chloro-3-(silyloxy)-2-en-1-ones

4.1 Functionalized Chlorophenols

4.2 Functionalized Chlorinated Biaryls and Chlorofluorenones

4.3 Functionalized Chlorochromenones

4.4 Functionalized 3-(Methylthio)chlorophenols

4.5 Functionalized 3-Chloromethylphenols

5 Conclusions

6 List of Abbreviations

Key words

silyl enol ethers - one-pot cyclizations - chlorine - arenes - heterocycles - regioselectivity

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