From Serendipity to Precision: Decoding the Enigma of Rearrangement in Scholl-Type Reactions for Programmable Cyclization

J Org Chem. 2024 Mar 15;89(6):4185-4190. doi: 10.1021/acs.joc.3c02050. Epub 2024 Feb 29.

Abstract

Rearrangements in the Scholl reaction have traditionally been serendipitous, lacking a systematic approach for synthesizing rearranged and cyclized products. This paper introduces a strategic pathway to achieve rearranged-cyclized thienotetrahelicene derivatives over direct-cyclized chrysenothiophene derivatives by finely modifying the reaction conditions and tuning the electronic properties in Scholl-type reaction precursors, tetraarylthiophenes. Through careful design principles, we demonstrate the programmable synthesis of these distinct products.