Waste-Free and Facile Solid-State Protection of Diamines, Anthranilic Acid, Diols, and Polyols with Phenylboronic Acid

• Published in: Chemistry : a European journal 2003-09, Vol.9 (17), p.4156-4161
• Main Authors: Kaupp, Gerd, Naimi-Jamal, M. Reza, Stepanenko, Vladimir
• Format: Article
• Language: English
• Subjects: diamines; environmentally benign; phenylboronic acid; polyols; solid-state reactions
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.200304793

Phenylboronic acid (2) reacts quantitatively by ball‐milling in the solid state with o‐phenylendiamine, 1,8‐diaminonaphthalene, anthranilic acid, pyrocatechol, pyrogallol, pinacol, bicyclic cis‐diols, mannitol, and inositol to form the five‐ or six‐membered cyclic phenylboronic amides or esters. Catalysts or other auxiliaries are strictly excluded as they are not required and would have to be removed after the reactions. These varied model reactions provide pure protected products without the necessity of further purifying workup and the potential for protection chemistry is demonstrated. Some of the reactions can also be quantitatively performed if stoichiometric mixtures of the reactants are co‐ground or co‐milled and heated to appropriate temperatures either below the eutectics or above the melting points. The temperatures are much higher in the latter case. Similar reactions in solution suffer from less than 100 % yield of the mostly sensitive compounds that are difficult to purify and thus create much waste. The hydrolysis (deprotection) conditions of the products are rather mild in most cases. Therefore, this particularly easy access to heteroboroles, heteroborolanes, heteroborinones, heteroborines, and heteroborinines is highly valuable for their more frequent use in protective syntheses. Diamines, amino acids, diols, and polyols are quantitatively protected by the solid‐state or solvent‐free reaction with phenylboronic acid without producing waste (see examples).