An umpolung strategy for intermolecular [2 + 2 + 1] cycloaddition of aryl aldehydes and nitriles: a facile access to 2,4,5-trisubstituted oxazoles.

We have described the first example of an umpolung strategy for intermolecular [2 + 2 + 1] cycloaddition between two aryl aldehydes and a nitrile under the influence of TMSOTf that proceeds through the formation of N-C, O-C and C-C bonds providing a simple synthetic protocol for obtaining 2,4,5-trisubstituted oxazoles.

Synthesis of C 3-symmetric star-shaped molecules containing α-amino acids and dipeptides via Negishi coupling as a key step.

We demonstrate a new synthetic strategy toward star-shaped C 3-symmetric molecules containing α-amino acid (AAA) derivatives and dipeptides. In this regard, trimerization and Negishi cross-coupling reactions are used as the key steps starting from readily available 4'-iodoacetophenone and L-serine. These C 3-symmetric molecules containing AAA moieties are useful to design new ligands suitable for asymmetric synthesis and peptide dendrimers.

Synthetic Approaches to Star-Shaped Molecules with 1,3,5-Trisubstituted Aromatic Cores.

Herein, we summarize the synthetic approaches that have been developed for the synthesis of star-shaped molecules. Typically, to design such highly functionalized molecules, simple building blocks are first assembled through trimerization reactions, starting from commercially available starting materials. Then, these building blocks are synthetically manipulated to generate extended star-shaped molecules. We also discuss the syntheses of star-shaped molecules that contain 2,4,6-trisubstituted 1,3,5-triazine or 1,3,5-trisubstituted benzene rings as a central core and diverse substituted styrene, phenyl, and fluorene derivatives at their periphery, which endows these molecules with extended conjugation. A variety of metal-catalyzed reactions, such as Suzuki, Buchwald-Hartwig, Sonogashira, Heck, and Negishi cross-coupling reactions, as well as metathesis, have been employed to functionalize a range of star-shaped molecules. The methods described herein will be helpful for designing a wide range of intricate compounds that are highly valuable in the fields of supramolecular chemistry and materials science. Owing to space limitations, we will not cover all of the publications on this topic. Instead, we will focus on examples that were reported by our research group and other relevant recent literature. Apart from the trimerization sequence, this Minireview has been structured based on the key reactions that were used to prepare the star-shaped molecules and other higher analogues. Finally, some examples that do not fit into this classification are discussed.

Design and synthesis of C 3-symmetric molecules bearing propellane moieties via cyclotrimerization and a ring-closing metathesis sequence.

We have developed an efficient synthetic strategy to assemble C 3-symmetric molecules containing propellane moieties as end groups and a benzene ring as a central core. The synthesis of these C 3-symmetric molecules involves simple starting materials. Our approach to C 3-symmetric compounds relies on a Diels-Alder reaction, cyclotrimerization and ring-closing metathesis as key steps.

Synthesis and Photophysical Properties of C 3-Symmetric Star-Shaped Molecules Containing Heterocycles Such as Furan, Thiophene, and Oxazole.

We report simple strategies to synthesize star-shaped molecules containing different heterocycles integrated with a number of variations. Here, cyclotrimerization, Vilsmeier-Haack reaction, Suzuki-Miyaura cross-coupling, and Van Leusen oxazole synthesis have been used as key steps to introduce diverse five-membered heterocycles such as furan, thiophene, and oxazole. More importantly, readily available starting materials such as thiophene, 2-formyl furan, and 2-acetyl furan were utilized. Also, the fluorescent behavior of these π-conjugated systems was studied. C 3-Symmetric molecules containing furan moieties show a stronger fluorescence than thiophene-containing star-shaped compounds.