Palladium-catalyzed intramolecular aromatic C-H acylation of 2-arylbenzoyl fluorides
The catalytic intramolecular cyclization of acyl fluorides using a Pd(OAc)2/PCy3 system is described. A wide range of 2-arylbenzoyl fluoride derivatives can be used as fluorenone precursors and the reaction proceeds via an intramolecular coupling between aromatic C-H bonds with acyl C-F bonds. The reaction can be applied to the synthesis of indenofluorenedione derivatives and to the construction of other molecules with fivemembered rings.
Intramolecular Vinylation of Aryl Rings by Vinyl Cations
A Lewis acid mediated intramolecular electrophilic vinylation of aryl rings by vinyl cations is reported. This reaction takes advantage of β-hydroxy-α-diazo ketones as vinyl cation precursors and provides good yields of tricyclic 1-indenones that contain
Fang, Jian,Brewer, Matthias
supporting information
p. 7384 - 7387
(2019/01/03)
Direct carbocyclizations of benzoic acids: Catalyst-controlled synthesis of cyclic ketones and the development of tandem aHH (acyl Heck-Heck) reactions
The formation of exo-methylene indanones and indenones from simple ortho-allyl benzoic acid derivatives has been developed. Selective formation of the indanone or indenone products in these reactions is controlled by choice of ancillary ligand. This new process has a low environmental footprint as the products are formed in high yields using low catalyst loadings, while the only stoichiometric chemical waste generated from the reactants in the transformation is acetic acid. The conversion of the active cyclization catalyst into the Hermman-Beller palladacycle was exploited in a one-pot tandem acyl Heck-Heck (aHH) reaction, and utilized in the synthesis of donepezil. Carboxylic acids in aHH: Simple ortho-allyl benzoic acid derivatives have been utilized in an acyl Heck (aH) reaction to selectively form indanones and indenones. The conversion of the active cyclization catalyst into the Hermman-Beller palladacycle was exploited in a one-pot tandem acyl Heck-Heck (aHH) reaction to form two sp 2-sp2 bonds of (E)-trisubstituted olefins.