The carbonylation of alkynes using CO to generate aurones is to date unknown. In this study, a palladium-catalyzed carbonylation of terminal aromatic alkynes and the waste hydrosilane, poly(methylhydrosiloxane) (PMHS), is carried out with 2-iodophenol using CO to produce aurones. A variety of terminal alkynes and substituted 2-iodophenols are transformed into aurones in good yields. Preliminary mechanistic studies indicate that silyl formate, generated from CO and PMHS, plays a crucial role in the carbonylation reaction.
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http://dx.doi.org/10.1002/cssc.202202365 | DOI Listing |
Molecules
November 2024
Department of General and Inorganic Chemistry, University of Pécs, Ifjúság u. 6., H-7624 Pécs, Hungary.
Palladium-catalyzed carbonylation reactions of -phenylene dihalides were studied using aminoethanols as heterobifunctional ,-nucleophiles. The activity of aryl-iodide and -bromide as well as the chemoselective transformation of amine and hydroxyl functionalities were studied systematically under carbonylation conditions. Aminocarbonylation can be selectively realized under optimized conditions, enabling the formation of amide alcohols, and the challenging alkoxycarbonylation can also be proved feasible, enabling amide-ester production.
View Article and Find Full Text PDFOrg Lett
December 2024
Leibniz-Institut für Katalyse e.V., Albert-Einstein-Straße 29a, 18059 Rostock, Germany.
Herein, we developed a mild and efficient palladium-catalyzed carbonylative Sonogashira coupling of aryl thianthrenium salts with aliphatic alkynes and benzyl acetylene toward alkynones and furanones. Various desired products were prepared in good yields with broad functional group tolerance including the bromide group. In the case of using benzyl acetylene, the corresponding furanones can be obtained in good yields under the same conditions with two molecules of CO inserted.
View Article and Find Full Text PDFChem Sci
December 2024
Leibniz-Institut für Katalyse e.V. Albert-Einstein-Straße 29a 18059 Rostock Germany
J Am Chem Soc
November 2024
Department of Chemistry, Emory University, Atlanta, Georgia 30322, United States.
We report an efficient total synthesis of (±)-phaeocaulisin A, a guaianolide sesquiterpene natural product possessing a complex tetracyclic skeleton embedded with an oxaspirolactone and a fused bicyclic lactone, four oxygen-containing stereocenters, and an 8-oxabicyclo[3.2.1]octane core.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
October 2024
Key Laboratory of Applied Surface and Colloid Chemistry & School of Chemistry and Chemical Engineering, Shaanxi Normal University, 620 West Chang'an Ave, Xi'an, 710119, China.
Ryanodane diterpenes are structurally complex natural products that are well-known for their high degree of oxidation and the challenges associated with synthesizing them within the terpene class. Herein, we present a two-stage synthetic strategy that draws inspiration from the broad biosynthesis of terpenes, allowing us to achieve the first chemical synthesis of garajonone, a ryanodane diterpenoid that occurs naturally at low abundance, as well as its epimer, 3-epi-garajonone. The key to this success lies in the rapid construction of the carbon framework of the target molecule by employing an early-stage palladium-catalyzed Heck/carbonylative esterification cascade annulation, followed by successive late-stage selective redox manipulation to establish the desired oxidation state of the molecule.
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