CpCo-Mediated Reactions of Cyclopropenones: Access to CpCo-Capped Benzoquinone Complexes

Abstract

The reaction of di(n-propyl)cyclopropenone ( 7), di(n-butyl)cyclopropenone ( 16), and bicyclo[12.1.0]pentadeca-1( 14)-en-7-yn-15-one (21) with CpCo(CO) 2 and CpCo(cod) yielded CpCo-complexed benzoquinone and cyclopentadienone derivatives. When 16 was reacted with CpCo(CO) 2 and a 10-fold surplus of 4-octyne, a mixture of CpCo-capped benzoquinone 25 and cyclopentadienone 26 was isolated. The reaction of cyclopropenone 16 containing a 13 C-labeled CO group with CpCo(CO) 2 yielded a CpCo-capped tetrakis(n-butyl)-p-benzoquinone with one 13 C nucleus per molecule as the main product. The mechanism of the formation of p-benzoquinone is discussed on the basis of the results of trapping and labeling experiments.

Oxidative Addition Promoted C–C Bond Cleavage in Rh-Mediated Cyclopropenone Activation: A DFT Study

“…Cyclopropenone derivatives , have the smallest cyclenone skeleton, and they have been widely engaged in transition-metal-catalyzed multifunctional molecule synthesis in recent decades, including alkenyl ketone, naphthol, butenolide, pyrrole-dione, and phenyl indene. The mechanism of these cyclopropenone activation reactions can be summarized by the following modes: When employing low-valent metals, such as Ru(0), , Rh­(I), − Cr­(II), Co­(I), − and Ni(0), − as catalysts, oxidative addition of the strained cyclopropenone backbone to the metal center produces a four-membered cyclorhometal butanone intermediate. In other cases, the transition metal acts as a Lewis acid to activate the carbonyl oxygen atom of cyclopropenone.…”

Cycloaddition Reactions of Cobalt-Complexed Macrocyclic Alkynes: The Transannular Pauson–Khand Reaction

“…These results are significant due to the importance of hydroquinone derivatives and the scarcity of hydroquinone or quinone syntheses mediated by cobalt–carbonyl complexes . The reported examples of participation of Co 2 (CO) 8 in hydroquinone/quinone synthesis are limited to dicobalt octacarbonyl-promoted intramolecular rearrangement of 1-(1,2-propadienyl)­cyclopropanols to 1,4-hydroquinones and synthesis of η 4 -quinone cobalt complexes .…”

Heterocycles from cyclopropenones

“…46 Cyclopropenones can form metal complexes via chelation with transition metals at the oxygen center or at the double bond. 47 2.1. Natural products containing cyclopropenone (1) and biological investigation of cyclopropenones Numerous extracted natural products have cyclopropenone moieties such as 2-(hydroxymethyl)-cycloprop-2-enone (penitricin) (A), 48 2-((8S,8aR)-8,8a-dimethyl-1,2,3,4,6,7,8,8aoctahydronaphthalen-2-yl)cycloprop-2-enone (B) and 2-((2R,4aR,8aS)-4a-methyl-8-methylenedecahydronaphthalen-2yl)cycloprop-2-enone (C) (Fig.…”