The technology—science interaction: Walter Reppe and cyclooctatetraene chemistry

Abstract

This is another paper about science and her powerful companion (technology), to use A. W. Hofmann's colourful phrase. Whereas most papers on the interaction of science and technology deal with the transfer of knowledge from academic science to industrial technology, this paper is about the contribution of an industrial researcher to academic chemistry. The boost Reppe's research gave to the study of aromaticity parallels the impact of the early synthetic dye chemistry on structural organic chemistry. This case study suggests that we cannot draw a clear distinction between ‘pure’ and ‘applied’ chemistry, in the laboratory at least.

One‐Pot Cannizzaro Cascade Synthesis of ortho‐Fused Cycloocta‐2,5‐dien‐1‐ones from 2‐Bromo(hetero)aryl Aldehydes

“…The paucity of direct single-pot/step procedures to such medium rings attests to the known issues associated with their synthesis; 5 they therefore provide a stringent test for strategy C. Although redox-based Cannizzaro reactions, including asymmetric and triggered C–C bond-forming versions, have recently been developed, 6 to the best of our knowledge, they have not been employed for carboannulation reactions to medium rings. Genuine single-pot/step procedures to eight-membered rings are very limited—Reppe’s historical catalytic access to cyclooctatetraene 7 and Murakami’s [4+2+2] approach 8 being notable exceptions. Modern alternatives frequently describe catalytic cyclizations that proceed with exquisitely high yields (for the final step).…”

One‐Pot Cannizzaro Cascade Synthesis of ortho‐Fused Cycloocta‐2,5‐dien‐1‐ones from 2‐Bromo(hetero)aryl Aldehydes

“…Herein, we describe the use of such as trategy for the formation of eight-membered rings. Thep aucity of direct single-pot/step procedures to such medium rings attests to the known issues associated with their synthesis; [5] they therefore provide as tringent test for strategy C. Although redox-based Cannizzaro reactions, including asymmetric and triggered C À Cb ond-forming versions,h ave recently been developed, [6] to the best of our knowledge,they have not been employed for carboannulation reactions to medium rings.G enuine single-pot/step procedures to eight-membered rings are very limited-Reppes historical catalytic access to cyclooctatetraene [7] and Murakamis [4+ +2+ +2] approach [8] being notable exceptions.Modern alternatives frequently describe catalytic cyclizationst hat proceed with exquisitely high yields (for the final step). Unfortunately,t heir overall synthetic efficiency is often compromised by the multistep syntheses required to obtain the cyclization precursors.…”