Inducing Enantioselectivity in a Dynamic Catalyst by Supramolecular Interlocking

Angewandte Chemie
Jan Felix Scholtes, Oliver Trapp

Abstract

The design of a new class of fluxional biphenyl bisphosphinite (BIBIPHOS) ligands decorated with amino acid-based diamide interaction sites is reported that undergo spontaneous desymmetrization. Hydrogenation of prochiral alkenes using Rh-BIBIPHOS results in enantiomeric ratios of up to 96:4 (R/S). This stereoconvergent behavior of the fluxional BIBIPHOS ligand is triggered by pronounced intermolecular interlocking of the recognition sites, leading to the formation of a supramolecular assembly, where the axial orientation of the biphenyl ligand backbone is governed by the chirality of the amino acid moieties. Stereoinduction during catalysis is decoupled from this process and occurs as an immediate consequence of the emergent behavior of the ligands. This supramolecular system is very robust and has the potential to be adopted for other ligand designs in enantioselective catalysis.

References

Mar 10, 2001·Nature·A SaghatelianM R Ghadiri
Oct 18, 2001·Journal of the American Chemical Society·L J PrinsD N Reinhoudt
Jul 12, 1996·The Journal of Organic Chemistry·William H. PirkleScott R. Wilson
Mar 30, 2006·Journal of the American Chemical Society·Martine WeisBernhard Breit
Feb 7, 2008·Chemical Communications : Chem Comm·Andy Ch Laungani, Bernhard Breit
May 30, 2008·Journal of the American Chemical Society·Jianfeng YuJon R Parquette
Dec 31, 2008·Angewandte Chemie·Tummanapalli SatyanarayanaHenri B Kagan
Feb 19, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Stefano CarboniUmberto Piarulli
Oct 4, 2011·Journal of the American Chemical Society·Paweł DydioJoost N H Reek
May 13, 2015·Chemical Society Reviews·Victor BlancoVanesa Marcos
Oct 8, 2016·Chemistry : a European Journal·Matea VlatkovićBen L Feringa
Mar 7, 2018·Angewandte Chemie·Katharina Marie WenzBernhard Breit
Aug 14, 2018·Chirality·Golo Storch, Oliver Trapp

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Citations

Jul 25, 2019·Chemistry : a European Journal·Jan Felix Scholtes, Oliver Trapp
Feb 20, 2021·Angewandte Chemie·Vanda DaškováBen L Feringa
Aug 5, 2021·Accounts of Chemical Research·Montserrat DiéguezChristina Moberg

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