Aryne Insertion Reactions into Carbon–Carbon σ-Bonds

Hiroto Yoshida; Ken Takaki

doi:10.1055/s-0031-1290401

Synlett, Inhaltsverzeichnis

Synlett 2012; 23(12): 1725-1732
DOI: 10.1055/s-0031-1290401

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Aryne Insertion Reactions into Carbon–Carbon σ-Bonds

Authors

Hiroto Yoshida*

Department of Applied Chemistry, Graduate School of Engineering, Hiroshima University, Higashi-Hiroshima 739-8527, Japan, Fax: +81(82)4247724 eMail: yhiroto@hiroshima-u.ac.jp
Ken Takaki

Department of Applied Chemistry, Graduate School of Engineering, Hiroshima University, Higashi-Hiroshima 739-8527, Japan, Fax: +81(82)4247724 eMail: yhiroto@hiroshima-u.ac.jp

Abstract

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Abstract

Diverse nucleophilic carbon–electrophilic carbon σ-bonds were found to undergo facile cleavage and to add across carbon–carbon triple bonds of arynes without the aid of transition-metal catalysts, leading to the direct introduction of different carbon functionalities into the ortho-positions of aromatic rings. Active methylene compounds including β-dicarbonyl compounds, α-cyanocarbonyl compounds, sulfonylacetonitrile, and malononitrile smoothly underwent the aryne insertion reactions, and, moreover, the reaction was applicable to fluorene and trifluoromethyl ketone derivatives. The total synthesis of cytosporone B and phomopsin C, depending upon the carbon–carbon bond cleavage reaction, is also described.

1 Introduction

2 β-Dicarbonyl Compounds

3 α-Cyanocarbonyl Compounds

4 Sulfonylacetonitrile and Malononitrile

5 Fluorenes

6 Trifluoromethyl Ketones

7 Total Synthesis of Cytosporone B and Phomopsin C

8 Conclusion

Key words

active methylene compounds - arynes - carbon–carbon bond cleavage - fluorenes - natural product synthesis - trifluoromethyl ketones

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Referenzen

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