Total synthesis reveals atypical atropisomerism in a small-molecule natural product, tryptorubin A.

Autor: Reisberg SH; Department of Chemistry, The Scripps Research Institute, La Jolla, CA 92037, USA., Gao Y; Department of Chemistry, The Scripps Research Institute, La Jolla, CA 92037, USA., Walker AS; Department of Biological Chemistry and Molecular Pharmacology, Harvard Medical School, Boston, MA 02115, USA., Helfrich EJN; Department of Biological Chemistry and Molecular Pharmacology, Harvard Medical School, Boston, MA 02115, USA., Clardy J; Department of Biological Chemistry and Molecular Pharmacology, Harvard Medical School, Boston, MA 02115, USA. jon_clardy@hms.harvard.edu pbaran@scripps.edu., Baran PS; Department of Chemistry, The Scripps Research Institute, La Jolla, CA 92037, USA. jon_clardy@hms.harvard.edu pbaran@scripps.edu.
Jazyk: angličtina
Zdroj: Science (New York, N.Y.) [Science] 2020 Jan 24; Vol. 367 (6476), pp. 458-463. Date of Electronic Publication: 2020 Jan 02.
DOI: 10.1126/science.aay9981
Abstrakt: Molecular shape defines function in both biological and material settings, and chemists have developed an ever-increasing vernacular to describe these shapes. Noncanonical atropisomers-shape-defined molecules that are formally topologically trivial but are interconvertible only by complex, nonphysical multibond torsions-form a unique subset of atropisomers that differ from both canonical atropisomers (e.g., binaphthyls) and topoisomers (i.e., molecules that have identical connectivity but nonidentical molecular graphs). Small molecules, in contrast to biomacromolecules, are not expected to exhibit such ambiguous shapes. Using total synthesis, we found that the peptidic alkaloid tryptorubin A can be one of two noncanonical atropisomers. We then devised a synthetic strategy that drives the atropospecific synthesis of a noncanonical atrop-defined small molecule.
(Copyright © 2020 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.)
Databáze: MEDLINE
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