Alkynedicobalt Complexes in γ-Carbonyl Cations and Cycloheptynedicobalt Complexes

Abstract

This Account describes our work on highly electrophilic γ-carbonyl cations featuring propargyldicobalt cations, cycloheptynedicobalt complexes, and the interconnection between the two systems.

1 Introduction

2 γ-Carbonyl Cations via Iron Allyl Cations

3 γ-Carbonyl Cations via Propargyldicobalt Cations

3.1 Synthesis of Velloziolide

3.2 Synthesis of Microstegiol

4 Synthesis of Cycloheptynedicobalt Complexes

4.1 Synthesis via γ-Carbonyl Cations

4.2 Cycloheptynedicobalt Complexes via [4+3] Cycloaddition Reactions

4.3 Cycloheptynedicobalt Complexes via Ring-Closing Meta­thesis

4.4 Cycloaddition Reactions on Cycloheptynedicobalt Complexes

4.5 Cycloheptynedicobalt Complexes via Intramolecular ­Nicholas Reactions

5 Dehydrotropylium Ion Co₂(CO)₆ Complex

6 Final Comments

Key words

carbocation - alkyne complexes - transition-metal - Umpolung - ring closure

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