Potentiality and Synthesis of O‐ and N‐Heterocycles: Pd‐Catalyzed Cyclocarbonylative Sonogashira Coupling as a Valuable Route to Phthalans, Isochromans, and Isoindolines

Abstract

Oxygen and Nitrogen-heterocyclic compounds are found in a vast number of natural substrates and biologically active molecules. In particular, phthalan, isochroman and isoindoline scaffolds are present in many classes of products such as antimicotics, antibiotics, antioxidants, pigments and fluorophores. Therefore several procedure dedicated to the buiding of such heterocycles have been developed. In this review a detailed analysis of literature data regarding these nuclei is described. Particular attention has been devoted to their biological and chemical potentialities and a deep investigation on the most important synthetic methods is reported. Cyclocarbonylative Sonogashira reaction of suitable alcohols and amides has been especially considered, since it represents a valuable and atom economic route to construct alkylidene phthalans, isochromans and isoindolines.Gianluigi Albano, born in Bari (Italy) in 1989, studied Chemistry at the University of Pisa (Italy), where he received his Master's Degree in February 2015. In November 2015 he started his PhD studies at the same university, under the supervision of Prof. Lorenzo Di Bari and Dr. Laura Antonella Aronica. His main research topics are focused on the synthesis and characterization of chiral conjugated oligomers for innovative optoelectronic applications and on the development of new protocols for the synthesis of heterocyclic compounds through transition metals-promoted reactions.Laura Antonella Aronica graduated cum laude in Chemistry in 1995 from the University of Pisa. In 1999 she obtained her Ph.D. in Chemical Sciences. During this period she spent six months as research assistant at University of Ottawa with Prof. Howard Alper. She is presently a researcher at the University of Pisa and her major research interests are concerned with organometallic chemistry directed towards organic synthesis and in particular with carbonylative cross coupling reactions and their application to the synthesis of heterocyclic compounds.

Preparation and Degradation of Rhodium and Iridium Diolefin Catalysts for the Acceptorless and Base-Free Dehydrogenation of Secondary Alcohols

“…In this context, it should be highlighted that the isoindoline skeleton is a part of a large variety of biologically active synthetic compounds, which have a wide range of applications in medicine. 28 …”

DMF as CO Surrogate in Carbonylation Reactions: Principles and Application to the Synthesis of Heterocycles

“…Compared with other CO surrogates-such as metal carbonyl complexes, whose use in stoichiometric amounts is problematic on a large scale as it may cause serious environmental pollution, or formaldehyde, whose manipulation is far from trivial-DMF is a cheap and easily accessible compound, typically used as a polar aprotic solvent in several organic reactions, easy to manipulate and also compatible for scale-up (Scheme 1a). Transition metal-catalyzed carbonylation reactions have acquired a prominent role in the field of the organic chemistry also for the synthesis of a multitude of useful carbonyl-containing heterocycles; in this context, we recently reported the application of cyclocarbonylative Sonogashira [19][20][21][22] and silylcarbocyclization reactions [23][24][25] for the synthesis of several classes of oxygen-and nitrogen-containing heterocycles. However, despite many advancements have been made in order to improve the feasibility and sustainability of these processes, the use of carbon monoxide represents a vexing problem which limits the widespread use of cyclocarbonylative reactions to some degree.…”

“…Transition metal-catalyzed carbonylation reactions have acquired a prominent role in the field of the organic chemistry also for the synthesis of a multitude of useful carbonylcontaining heterocycles; in this context, we recently reported the application of cyclocarbonylative Sonogashira [19][20][21][22] and silylcarbocyclization reactions [23][24][25] for the synthesis of several classes of oxygen-and nitrogen-containing heterocycles. However, despite many advancements have been made in order to improve the feasibility and sustainability of these processes, the use of carbon monoxide represents a vexing problem which limits the widespread use of cyclocarbonylative reactions to some degree.…”

Palladium Nanoparticles Supported on Smopex-234® as Valuable Catalysts for the Synthesis of Heterocycles

“…Isochroman [19][20][21] (Figure 1b) is the structural unit of a large number of compounds found in olive oil [22][23][24], leaves [25], and fungi [26][27][28][29][30]. Many isochromans exhibit anti-inflammatory [31][32][33], antibacterial [34,35], antifungal [36], antioxidant, and antiplatelet [37,38] activities, while some show cytotoxicity toward human cancer cell lines [39,40] and are used in the treatment of migraine headaches [41].…”