Photothermal Conversion by Carbon Black Facilitates Aryl Migration by Photon‐Promoted Temperature Gradients
Megan E. Matter, Lejla Čamdžić, Erin E. Stache
Abstract
The Newman Kwart Rearrangement (NKR) offers an efficient and high-yielding method for producing substituted thiophenols from phenols. While an industrially important protocol, it suffers from high activation energy barriers (35-43 kcal/mol), requiring the use of extreme temperatures (>200 °C) and specialty equipment. This report details a highly efficient and straightforward method for facilitating the NKR using photothermal conversion. This underused, unique reactivity pathway arises from the irradiation of nanomaterials that relax via a non-radiative decay pathway to generate intense thermal gradients. We show carbon black (CB) can be an inexpensive and abundant photothermal agent under visible light irradiation to achieve a facile NKR under mild conditions. The scope includes a wide array of stereo- and electronically diverse substrates with increasing difficulty of rearrangement, including BHT and BINOL as effective substrates. Furthermore, we demonstrate the unique application for temporal control in a thermal reaction and tunability of thermal gradients by modulating light intensity. Ultimately, photothermal conversion enables high-temperature reactions with simple, visible light irradiation.