Regio- and diastereoselective intermolecular [2+2] cycloadditions photocatalysed by quantum dots

Yishu Jiang, Chen Wang, Cameron R. Rogers, Mohamad S. Kodaimati, Emily A. Weiss

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

Light-driven [2+2] cycloaddition is the most direct strategy to build tetrasubstituted cyclobutanes, core components of many lead compounds for drug development. Significant advances in the chemoselectivity and enantioselectivity of [2+2] photocycloadditions have been made, but exceptional and tunable diastereoselectivity and regioselectivity (head-to-head versus head-to-tail adducts) is required for the synthesis of bioactive molecules. Here we show that colloidal quantum dots serve as visible-light chromophores, photocatalysts and reusable scaffolds for homo- and hetero-intermolecular [2+2] photocycloadditions of 4-vinylbenzoic acid derivatives, including aryl-conjugated alkenes, with up to 98% switchable regioselectivity and 98% diastereoselectivity for the previously minor syn-cyclobutane products. Transient absorption spectroscopy confirms that our system demonstrates catalysis triggered by triplet–triplet energy transfer from the quantum dot. The precisely controlled triplet energy levels of the quantum dot photocatalysts facilitate efficient and selective heterocoupling, a major challenge in direct cyclobutane synthesis.

Original languageEnglish
Pages (from-to)1034-1040
Number of pages7
JournalNature chemistry
Volume11
Issue number11
DOIs
Publication statusPublished - Nov 1 2019

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Cyclobutanes
Cycloaddition
Semiconductor quantum dots
Regioselectivity
Photocatalysts
Lead compounds
Enantioselectivity
Alkenes
Chromophores
Absorption spectroscopy
Scaffolds
Energy transfer
Electron energy levels
Catalysis
Olefins
Derivatives
Molecules
Acids
Pharmaceutical Preparations

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)

Cite this

Regio- and diastereoselective intermolecular [2+2] cycloadditions photocatalysed by quantum dots. / Jiang, Yishu; Wang, Chen; Rogers, Cameron R.; Kodaimati, Mohamad S.; Weiss, Emily A.

In: Nature chemistry, Vol. 11, No. 11, 01.11.2019, p. 1034-1040.

Research output: Contribution to journalArticle

Jiang, Yishu ; Wang, Chen ; Rogers, Cameron R. ; Kodaimati, Mohamad S. ; Weiss, Emily A. / Regio- and diastereoselective intermolecular [2+2] cycloadditions photocatalysed by quantum dots. In: Nature chemistry. 2019 ; Vol. 11, No. 11. pp. 1034-1040.
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