Palladium-Catalyzed Acetoxylation of γ-Dehydro-aryl-himachalene: The Synthesis of a Novel Allylic Acetoxylated Sesquiterpene and a π-Allyl Palladium(II) Complex
Issam Louchachha,
Abdelmajid Faris,
Youssef Edder,
Ali Hasnaoui,
Anna Kozakiewicz-Piekarz,
Abdelkarim Ait Mansour,
Brahim Boualy,
Rachid Salghi,
Khalil Azzaoui,
Rachid Sabbahi,
Ashwag S. Alanazi,
Mohamed Hefnawy,
Belkheir Hammouti,
Abdallah Karim,
Mustapha Ait Ali
Affiliations
Issam Louchachha
Laboratory of Molecular Chemistry, Faculty of Sciences Semlalia, Cadi Ayyad University, B.P. 2390, Marrakech 40001, Morocco
Abdelmajid Faris
Laboratory of Molecular Chemistry, Faculty of Sciences Semlalia, Cadi Ayyad University, B.P. 2390, Marrakech 40001, Morocco
Youssef Edder
Laboratory of Molecular Chemistry, Faculty of Sciences Semlalia, Cadi Ayyad University, B.P. 2390, Marrakech 40001, Morocco
Ali Hasnaoui
Laboratory of Molecular Chemistry, Faculty of Sciences Semlalia, Cadi Ayyad University, B.P. 2390, Marrakech 40001, Morocco
Anna Kozakiewicz-Piekarz
Department of Biomedical Chemistry and Polymers, Faculty of Chemistry, Nicolaus Copernicus University in Toruń, Gagarina 7, 87-100 Torun, Poland
Abdelkarim Ait Mansour
Laboratory of Applied Chemistry and Environment, ENSA, University Ibn Zohr, P.O. Box 1136, Agadir 80000, Morocco
Brahim Boualy
Multidisciplinary Research and Innovation Laboratory, Faculté Polydisciplinaire de Khouribga, Université Sultan Moulay Slimane, Khouribga 23000, Morocco
Rachid Salghi
Laboratory of Applied Chemistry and Environment, ENSA, University Ibn Zohr, P.O. Box 1136, Agadir 80000, Morocco
Khalil Azzaoui
Euromed Research Center, Euromed Polytechnic School, Euromed University of Fes, Eco-Campus, Fes Meknes Road, Fes 30030, Morocco
Rachid Sabbahi
Euromed Research Center, Euromed Polytechnic School, Euromed University of Fes, Eco-Campus, Fes Meknes Road, Fes 30030, Morocco
Ashwag S. Alanazi
Department of Pharmaceutical Sciences, College of Pharmacy, Princess Nourah bint Abdulrahman University, Riyadh 11671, Saudi Arabia
Mohamed Hefnawy
Department of Pharmaceutical Chemistry, College of Pharmacy, King Saud University, Riyadh 11451, Saudi Arabia
Belkheir Hammouti
Euromed Research Center, Euromed Polytechnic School, Euromed University of Fes, Eco-Campus, Fes Meknes Road, Fes 30030, Morocco
Abdallah Karim
Laboratory of Molecular Chemistry, Faculty of Sciences Semlalia, Cadi Ayyad University, B.P. 2390, Marrakech 40001, Morocco
Mustapha Ait Ali
Laboratory of Molecular Chemistry, Faculty of Sciences Semlalia, Cadi Ayyad University, B.P. 2390, Marrakech 40001, Morocco
Allylic oxygenated derivatives of himachalenes are highly valued molecules due to their potential applications in perfumery, cosmetics, and pharmaceuticals. Previous attempts at catalyzed allylic oxidation of himachalenes led to the formation of a very stable η3-allyl palladium complex, preventing any further reaction development. Herein, we present the first successful palladium-catalyzed synthesis of a novel allylic acetoxylated derivative of himachalenes. This reaction was achieved by incorporating an aromatic ring into the substrate structure. The resulting intermediate complex was isolated and characterized using nuclear magnetic resonance spectroscopy and X-ray crystallography. Density functional theory (DFT) calculations were performed to compare the reactivity of the newly synthesized complex with previously reported ones. The theoretical results confirm that the introduction of an aromatic ring enhances the reactivity of the η³-allyl palladium complex, thereby facilitating the desired transformation.
