Ho Yun Hwang

Unusually Stable, Versatile, and Pure Arenediazonium Tosylates: Their Preparation, Structures, and Synthetic Applicability

A new, simple, and effective method for the diazotization of a wide range of arylamines has been developed by using a polymer-supported diazotization agent in the presence of p-toluenesulfonic acid. Various pure arenediazonium tosylates with unusual stabilities can be easily prepared by this method. As a result, these salts are useful and versatile substrates for subsequent transformations, such as halogenation and Heck-type reactions. The unusual stabilities of arenediazonium tosylates are also preliminarily discussed with their X-ray structures.

A simple and efficient procedure for diazotization-iodination of aromatic amines in aqueous pastes by the action of sodium nitrite and sodium hydrogen sulfate

One of the most widely used methods of synthesis of aromatic iodides is based on diazotization–iodina-tion of aromatic amines. The diazotization is generally carried out using accessible sodium nitrite in strongly acidic medium at reduced temperature [1–5]. Alter-native procedures involve more expensive alkyl nitrites as diazotizing agents in the presence of diiodomethane or other sources of iodine [6, 7]. We previously pro-posed simple procedures for diazotization–iodination with sodium nitrite at room temperature in weakly acidic media created by

Self-selected formation of single discrete supramolecules with flexible, bidentate ligands in the coordination-driven self-assembly

Flexible donor ligands like 1,2-bis(3-pyridyl)ethyne or 1,4-bis(3-pyridyl)-1,3-butadiyne self-assemble into discrete 2-D supramolecules instead of infinite networks upon combination with organoplatinum 90, 120, and 180 degree acceptor units. These systems are unique examples of versatile pyridine donors adjusting their bonding directionality to accommodate rigid platinum acceptors in the formation of closed macrocycles. Discrete, nanoscopic 3-D cages are also prepared in high yield via coordination-driven self-assembly from bidentate 3-substituted pyridines and tripod organoplatinum acceptors. Flexible, bidentate 3-substituted pyridine donors and a rigid organopalladium acceptor are also exclusively self-assembled into discrete 2-D macrocycles. Moreover, discrete supramolecules are successfully prepared from ambidentate donor ligands and platinum containing acceptors. Despite the possibility of forming more than one product, ambidentate ligands prefer to self-assemble predominantly into one species. Flexible, ambidentate pyridyl-carboxylate based donor ligands like sodium 3-(3-pyridyl)benzoate, sodium 4-(3-pyridyl)benzoate and potassium 4-(3-pyridyl)ethynylbenzoate self-assemble into discrete [2+2] macrocyclic species instead of infinite networks when combined with a 90 degree organoplatinum acceptor. In each case only one isomeric ensemble is selectively formed in high yield. All products are characterized by electrospray ionization mass spectrometry (ESI-MS), 31P{1H} and 1H NMR spectroscopy. They are the first examples of discrete supramolecules incorporating flexible, bidentate donor ligands. Despite their potential versatility, these flexible donors adjust their bonding directionality to accommodate a rigid acceptor in the formation of one discrete ensemble.