Selective Isomerization via Transient Thermodynamic Control: Dynamic Epimerization of trans to cis Diols

Christian J. Oswood, David W.C. MacMillan

Research output: Contribution to journalArticlepeer-review

1 Scopus citations

Abstract

Traditional approaches to stereoselective synthesis require high levels of enantio- and diastereocontrol in every step that forms a new stereocenter. Here, we report an alternative approach, in which the stereochemistry of organic substrates is selectively edited without further structural modification, a strategy with the potential to allow new classes of late-stage stereochemical manipulation and provide access to rare or valuable stereochemical configurations. In this work, we describe a selective epimerization of cyclic diols enabled by hydrogen atom transfer photocatalysis and boronic acid mediated transient thermodynamic control, selectively generating less stable cis products from the otherwise favored trans isomers. A range of substitution patterns and ring sizes are amenable to selective isomerization, including stereochemically complex polyols such as estriol, as well as syn to anti epimerization of acyclic vicinal diols. Moreover, this strategy has enabled the divergent epimerization of saccharide anomers, providing access to distinct sugar isomers from α- or β-configured glycosides.

Original languageEnglish (US)
Pages (from-to)93-98
Number of pages6
JournalJournal of the American Chemical Society
Volume144
Issue number1
DOIs
StatePublished - Jan 12 2022

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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