TY - JOUR
T1 - Selective Isomerization via Transient Thermodynamic Control
T2 - Dynamic Epimerization of trans to cis Diols
AU - Oswood, Christian J.
AU - MacMillan, David W.C.
N1 - Publisher Copyright:
© 2021 American Chemical Society.
PY - 2022/1/12
Y1 - 2022/1/12
N2 - 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.
AB - 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.
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U2 - 10.1021/jacs.1c11552
DO - 10.1021/jacs.1c11552
M3 - Article
C2 - 34933555
AN - SCOPUS:85121981286
SN - 0002-7863
VL - 144
SP - 93
EP - 98
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 1
ER -