Chemo- and stereoselective intermolecular [2 + 2] photocycloaddition of conjugated dienes using colloidal nanocrystal photocatalysts

Yishu Jiang, Muwen Yang, Yue Wu, Rafael López-Arteaga, Cameron R. Rogers, Emily A. Weiss*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

21 Scopus citations

Abstract

The use of visible-light photosensitizers to power [2 + 2] photocycloadditions that produce complex tetrasubstituted cyclobutanes is a true success of photochemistry, but the scope of this reaction has been limited to activated α,β-unsaturated carbonyls. This paper describes selective intermolecular homo- and hetero-[2 + 2] photocycloadditions of terminal and internal aryl-conjugated dienes—substrates historically unsuited for this reaction because of their multiple possible reaction pathways and product configurations—through triplet-triplet energy transfer from CdSe nanocrystal photocatalysts to generate valuable and elusive syn-trans aryl vinylcyclobutanes. The negligible singlet-triplet splitting of nanocrystals' excited states allows them to drive the [2 + 2] pathway over the competing [4 + 2] photoredox pathway, a chemoselectivity not achievable with any known molecular photosensitizer. Reversible tethering of the cyclobutane product to the nanocrystal surface results in near-quantitative yield of the syn-trans product. Flat colloidal CdSe nanoplatelets produce cyclobutanes coupled at the terminal alkenes of component dienes with up to 89% regioselectivity.

Original languageEnglish (US)
Pages (from-to)106-116
Number of pages11
JournalChem Catalysis
Volume1
Issue number1
DOIs
StatePublished - Jun 17 2021

Keywords

  • SDG13: Climate action
  • SDG7: Affordable and clean energy
  • SDG9: Industry, innovation, and infrastructure
  • aryl-conjugated dienes
  • cycloaddition
  • nanoplatelet
  • photocatalysis
  • quantum dot
  • syn-trans aryl vinylcyclobutanes
  • templating

ASJC Scopus subject areas

  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Chemistry (miscellaneous)

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