Inter- and Intramolecular [2+2+2] Cycloaddition of Alkyne Triple Bonds to the Carbonyl Function of Aldehydes and Ketones Enabled by η5-Cyclopentadienylcobalt(L)(L′)

Véronique Colovray-Gotteland; Daniel F. Harvey; Barry M. Johnson; Christopher S. Ung; K. Peter C. Vollhardt

doi:10.1055/s-0040-1707322

Synlett, Table of Contents

Synthesis 2021; 53(04): 699-712
DOI: 10.1055/s-0040-1707322

paper

Inter- and Intramolecular [2+2+2] Cycloaddition of Alkyne Triple Bonds to the Carbonyl Function of Aldehydes and Ketones Enabled by η⁵-Cyclopentadienylcobalt(L)(L′)

Véronique Colovray-Gotteland

,

Daniel F. Harvey

,

Barry M. Johnson

,

Christopher S. Ung

,

K. Peter C. Vollhardt ∗

Abstract

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Abstract

1,7-Octadiyne underwent [2+2+2] cycloaddition to acetone in the presence of η⁵-cyclopentadienylcobalt(L)(L′) complexes to give (η⁵-cyclopentadienyl)[(1,4,4a,8a-η⁴)-5,6,7,8-tetrahydro-3,3-dimethyl-3H-2-benzopyran]cobalt, in which the two triple bonds and the carbonyl moiety have combined to engender a 2H-pyran ring complexed to CpCo. The scope of this reaction was explored, including cocyclizations of ynals and ynones with bis(trimethylsilyl)acetylene, as well as all-intramolecular reorganizations of α,ω-diynals and -diynones. Two major trajectories were observed in the case of aldehydes, the (often minor) [2+2+2] pathway and a competing trail featuring a formal 1,5-hydride shift that results in CpCo–dienones. The latter is obviated for ketone substrates. Preliminary chemistry of selected complexes uncovered unprecedented reactions, such as acid-catalyzed ring openings and additions of amines, the latter providing access to novel carbon frames.

Key words

alkynes - carbonyl compounds - cobalt - cycloaddition - 2H-pyrans

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References

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