Photothermal Conversion by Carbon Black Facilitates Aryl Migration by Photon-Promoted Temperature Gradients

Megan E. Matter, Lejla Čamdžić, Erin E. Stache

Research output: Contribution to journalArticlepeer-review

3 Scopus citations

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.

Original languageEnglish (US)
Article numbere202308648
JournalAngewandte Chemie - International Edition
Volume62
Issue number40
DOIs
StatePublished - Oct 2 2023
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • General Chemistry
  • Catalysis

Keywords

  • Arenes
  • Carbon Black
  • Photothermal Conversion
  • Rearrangements
  • Temporal Heating

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