A Career in Catalysis: Howard Alper

Abstract

Still going strong in his seventies, Professor Howard Alper continues to make an impact on chemistry internationally. This Account highlights some of his key scientific achievements in catalysis. What began as a fundamental interest in the chemistry of metal carbonyls and their activity modes, evolved into a versatile program addressing some of the most significant and challenging issues in catalysis. Using well-defined metal carbonyl complexes, he and his lab were able to make fundamental insights into diverse transformations involving the catalytic properties of metal carbonyls, including carbonylative ring expansions. His creative and truly interdisciplinary research in catalysis has also resulted in notable contributions to carbonylation, hydrofunctionalization, and cycloaddition chemistry.

Photoinduced Copper-Catalyzed Radical Aminocarbonylation of Cycloketone Oxime Esters

“…Transition metal-catalyzed carbonylation reaction represents one of the most powerful and useful methods for the synthesis of organic carbonyl compounds . In the traditional transition metal-catalyzed ionic carbonylation processes of alkyl halides, some competitive reactions such as β-hydride elimination and isomerization of organometallic species are often encountered.…”

Cobalt catalysed aminocarbonylation of thiols in batch and flow for the preparation of amides

“…This group developed as well alkoxycarbonylations using high CO pressures, high temperature and long reaction times. 6 Furthermore, it was observed that these reactions were not operative under anhydrous conditions or with other catalysts such as Fe 3 (CO) 12 and [Rh(CO) 2 ] 2 .…”

Pd-Catalyzed Decarboxylative Cycloaddition of Vinylethylene Carbonates with Isothiocyanates

“…Sulfur-containing compounds have been discovered in numerous natural products and also figure among agrochemicals, pharmaceuticals, and functional materials. Among the commonly used heterocumulenes, isothiocyanates are easily available and have been used to construct diverse scaffolds of S-containing heterocycles by transition-metal-catalyzed cyclization of isothiocyanates. , The Pd-catalyzed cycloaddition of vinylethylene carbonates with isocyanates and photogenerated ketenes have been applied to form both five- and seven-membered heterocycles (Scheme ). Unlike previous Pd-catalyzed cycloaddition of isothiocyanates where the C–S bond is usually formed, formation of the C–N bond could be realized in the Pd-catalyzed decarboxylative cycloaddition of VECs with isothiocyanates.…”

“…Among the commonly used heterocumulenes, isothiocyanates are easily available and have been used to construct diverse scaffolds of S-containing heterocycles by transition-metal-catalyzed cyclization of isothiocyanates. , The Pd-catalyzed cycloaddition of vinylethylene carbonates with isocyanates and photogenerated ketenes have been applied to form both five- and seven-membered heterocycles (Scheme ). Unlike previous Pd-catalyzed cycloaddition of isothiocyanates where the C–S bond is usually formed, formation of the C–N bond could be realized in the Pd-catalyzed decarboxylative cycloaddition of VECs with isothiocyanates. Herein, we report an efficient synthesis of 1,3-oxazolidine-2-thiones by Pd-catalyzed [3 + 2] cycloaddition of vinylethylene carbonates with isothiocyanates.…”