José Barluenga, emeritus professor at the University of Oviedo, passed away on September 7, 2016. Barluenga was one of the leading Spanish chemists of his generation, with research interests including metal-mediated activation of alkenes and alkynes, β-functionalized organolithium compounds, iodination reactions, asymmetric Diels–Alder reactions, carbene complexes, and cross-coupling reactions. Early studies from Barluenga's laboratory pioneered the field of metal-mediated activation of alkenes and alkynes towards nucleophiles. He also documented the relevant role of azadienes as precursors for nitrogen-containing organic molecules. His fascination with this class of compounds derived from his postdoctoral work and remained a central theme throughout his initial scientific career. His studies on β-functionalized organolithium compounds brought this elusive and highly reactive class of reagents into the mainstream of organic synthesis. In the mid-1980s, Barluenga prepared bis(pyridine)iodonium(I) tetrafluoroborate IPy2BF4, which is nowadays known as Barluenga's reagent. In addition to establishing the synthetic merit and potency of this reagent in different iodination strategies, he initiated incursions into iodination as a tool for “green” carbon–carbon and carbon–heteroatom coupling reactions. His design of new enantiopure 2-aminodienes culminated in the demonstration that asymmetric Diels–Alder reactions can be accomplished by locating chiral information at the diene. Following his characteristic desire to constantly push the existing boundaries of reactivity, Barluenga then moved on to the application of Fischer-type carbene complexes of Group 6 metals, including the use of nonstabilized carbene complexes to produce precursors for molecular materials. In his final years, he became interested in new concepts for cross-coupling transformations. Here, he explored the potential of palladium-catalyzed C–N coupling reactions to trigger complex synthetic cascades, often directed to the preparation of privileged heterocyclic scaffolds. Finally, he introduced N-tosylhydrazones as a safe alternative to diazo compounds for enabling unconventional metal-free coupling reactions. Barluenga received many national and international awards and distinctions. He was enthusiastically involved in the education of a total of 120 graduate students and a large number of postdoctoral workers, and proudly followed their careers. More than fifteen of his former co-workers have become full professors at various Spanish universities. Barluenga advanced the development of the chemistry community in Spain, and was a strong public advocate of academic research. His highly productive and prominent career comprises more than 600 publications and took place concurrently with the advent of Spanish science during the latter part of the 20th century. He was largely responsible for the reputation gained by the Spanish chemical community, while acting as a charismatic ambassador for the new generation of young Spanish scientists in his frequent visits to top universities, industrial research laboratories, and at conferences worldwide. Above all, he was always at home in his laboratories, where he displayed his never-ending enthusiasm for research, which he liked to refer to as his particular “journey to Ithaca”. José Barluenga was a proud family man and always treasured the free time he spent with his wife and children. Only his devotion to his family could partially interrupt the exhaustive dedication to science by this uniquely passionate, generous, and gifted chemist. His physical presence will be sadly missed, but his scientific legacy and his personality, commitment, and talent will continue to be remembered by all who had the privilege to interact with him.
Read full abstract