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
,
This work was funded by the National Institutes of Health (NIH, GM 22479), the National Science Foundation (NSF, CHE 0907800), and the University of California at Berkeley.


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.

Supporting Information



Publication History

Received: 07 September 2020

Accepted after revision: 14 September 2020

Publication Date:
12 October 2020 (online)

© 2020. Thieme. All rights reserved

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