One-Pot Suzuki–Miyaura C–C Coupling Reaction versus Stepwise Reaction Involving Isolated Synthesized Catalyst Addition

Abstract

Suzuki–Miyaura coupling reactions are well-known among the most versatile catalytic C–C bond formation reactions. Two different routes of C–C bond Suzuki–Miyaura coupling reactions for the undergraduate organic chemistry laboratory courses have been designed and explained. A two-step reaction involving a catalyst preparation as the first step and a C–C bond formation as the second step of the reaction was introduced. A one-pot catalytic reaction was also introduced in comparison. The goals for such designation of two different routes for Suzuki–Miyaura cross-coupling reactions were to allow undergraduate students to understand the concept of Suzuki–Miyaura cross-coupling reactions and also to allow the students to experience the ease by which a one-pot reaction can provide a researcher the best way to follow the organic synthesis. During the reactions processes, the students will learn to carry out reactions under a Schlenk line, working with air-sensitive compounds in a glovebox. They will also have the opportunity to compare the reaction approaches in many different ways: for example, cost, time, handling materials, safety, and straightforwardness.

Ethynylated Acene Synthesis and Photophysics for an Organic Chemistry Laboratory Course

“…The mention of small molecule organic chromophores in the chemical education literature has mostly been limited to the analysis of molecular photophysics and/or reaction kinetics − and generally does not include the preparation of conjugated small molecules in combination with photophysical analysis. When considering the variety of substitution, elimination, and coupling reactions that meet the requirements for air- and water-free techniques, most of the reactions with low molecular weight species do not yield colorful products. − Although UV–vis analysis could be performed on many of these phenyl, styrenyl, biphenyl, etc. products, reaction success cannot be determined by visual inspection, and even if products are colored, the reactions are often muddied by the brown color of catalysts.…”

Synthesis and Characterization of a Metal-Free Organic Dye-Sensitizer for Solar Cell: An Advanced Organic Chemistry Research-Based Laboratory

“…The dye is prepared via three synthetic steps according to Scheme . The donor moiety, compound 2 , ( N -phenyl-4-(pyren-2-yl))- N -[4-(pyren-2-yl)­phenyl]­aniline, is synthesized using the Suzuki–Miyaura cross coupling reaction by reacting 4,4′-dibromotriphenylamine with pyrene-1-boronic acid in the presence of ethanol, THF, and the catalyst, Pd­(PPh 3 ) 4 . − Preparation of compound 3 , the intermediate, 4-{bis-[4-(pyren-2-yl)­phenyl]­amino}­benzaldehyde, is accomplished using the Vilsmeier–Haak reaction by reacting compound 2 with phosphorus oxychloride in N,N- dimethylformamide (DMF) at 0 °C. − Finally, the introduction of the acceptor group to produce the organic dye, (2 E )-3-(4-bis­[4-(pyren-2-yl)­phenyl]­amino)­phenyl-2-cyanoprop-2-enoic acid, is achieved using the Knoevenagel reaction by reacting 3 with cyanoacetic acid in acetonitrile and piperidine. − The progress of the reactions is monitored by TLC, and the purifications of the crude intermediates, and product, are conducted by column chromatography, and recrystallization techniques. The synthesized dye is characterized by NMR and IR spectroscopy.…”

“…The primary goal of this lab is to introduce students to the application of organic synthesis in material science, and renewable energy research. It also provides students with an opportunity to practice organic synthetic reactions utilized in traditional organic synthesis research laboratories such as Suzuki–Miyaura coupling, − Vilsmeier–Haack formylation, − and Knoevenagel reactions. − Furthermore, students get acquainted with the Vilsmeier–Haack formylation reaction which has never appeared in this Journal before to the best of our knowledge. Also, they practice and learn how to perform cyclic voltametric and photophysics measurements which are experimental techniques applied in DSSC research.…”

Exploring the Effect of Phosphine Ligand Architecture on a Buchwald–Hartwig Reaction: Ligand Synthesis and Screening of Reaction Conditions

“…Palladium-catalyzed coupling reactions are fundamental methods in synthetic organic chemistry . Introductory-level textbooks have recently begun to include discussion of this area, and many instructional laboratory exercises are now available for showcasing the Suzuki–Miyaura coupling − and related reactions. − In contrast to these C–C σ-bond forming processes, the Pd-catalyzed coupling of amines with organic halides to form C–N σ-bonds, termed the Buchwald–Hartwig amination (BHA), is underrepresented in the instructional literature. Indeed, despite its broad utility, − only three instructional laboratory modules focusing on the BHA reaction have been reported.…”