Allyl carbonates undergo palladium-catalyzed decarboxylative allylation of trifluoroethyl phenyl sulfones. The success of the allylation, which is not efficient under typical strong base-mediated conditions, is the result of mild conditions thanks to a progressive delivery of ethoxide. Indeed, ethyl allyl carbonates act as a latent source of ethoxide for generation of the trifluoroethyl carbanion that reacts with the π-allylpalladium complex. The utility of the method is illustrated in a new approach to difluoromethyl compounds.
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http://dx.doi.org/10.1021/ol302589w | DOI Listing |
Chem Res Toxicol
December 2024
Department of Chemistry, Vanderbilt University, Nashville, Tennessee 37235, United States.
The algal macrolide goniodomin A (GDA) undergoes ring-cleavage under unusually mild, alkaline conditions to form mixtures of stereoisomers of seco acids GDA-sa and iso-GDA-sa. In the primary fragmentation pathway, opening of the macrolide ring occurs by displacement of the carboxyl group by a base-catalyzed attack of the C32 hemiketal hydroxy group on C31, yielding an oxirane-carboxylic acid, named goniodomic acid. The oxirane ring is unstable, undergoing solvolytic opening to form mainly GDA-sa.
View Article and Find Full Text PDFOrg Lett
December 2024
College of Advanced Interdisciplinary Science and Technology, Henan University of Technology, Zhengzhou 450001, China.
We developed a novel, metal-free catalytic system for synthesizing a broad range of itaconates using α-ketoacids and allylic acetate. This method, leveraging phosphine and Mes-Acr(BF) catalysts, has proven versatile, enabling the efficient itaconation of peptides, the synthesis of bioactive itaconates, and the preparation of an itaconate-based bio-orthogonal probe.
View Article and Find Full Text PDFOrg Lett
December 2024
Institut für Chemie, Universität Oldenburg, D-26129 Oldenburg, Germany.
Optically active spirocycles were prepared in a sequence of two palladium-catalyzed reactions. In the first step, racemic α-(-iodophenyl)-β-oxo allyl esters were submitted to the palladium-catalyzed decarboxylative asymmetric allylic alkylation reaction, furnishing the α-allylated products with a quaternary stereocenter with good yields and enantioselectivities. Subsequently, these intermediate products were converted in a Heck reaction yielding the spirocyclic structures as a mixture of - and -cyclic regioisomers.
View Article and Find Full Text PDFJ Am Chem Soc
December 2024
Graduate School of Pharmaceutical Sciences, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Euphorbialoid A () belongs to the rare diterpenoid family of premyrsinanes and exhibits potent anti-inflammatory effects. The 5/7/6/3-membered carbocycle (ABCD-ring) of contains 11 contiguous stereocenters and seven oxygen-containing functional groups. Moreover, four of the six hydroxy groups of are concentrated in the southern sector and flanked by four structurally different acyl groups.
View Article and Find Full Text PDFOrg Biomol Chem
November 2024
Department of Chemistry, Jilin Institute of Chemical Technology, 45 Chengde Street, Jilin City, 132022, People's Republic of China.
Highly regioselective tungsten (W)-catalyzed decarboxylative allylic amination of allylic carbamates has been developed. Allylic carbamates can be generated from readily available allylic alcohols and commercially available isocyanates. In the presence of a tungsten catalyst, branched allylic amines could be obtained in moderate to good yields with excellent regioselectivities (b/l > 20 : 1), and CO is the only byproduct.
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