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Supramolecular Bidentate Ligands by Metal‐Directed in situ Formation of Antiparallel β‐Sheet Structures and Application in Asymmetric Catalysis
Author(s) -
Laungani Andy C.,
Slattery John M.,
Krossing Ingo,
Breit Bernhard
Publication year - 2008
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200800359
Subject(s) - antiparallel (mathematics) , supramolecular chemistry , catalysis , denticity , chemistry , hydroformylation , supramolecular catalysis , combinatorial chemistry , beta sheet , self assembly , supramolecular assembly , stereochemistry , crystallography , metal , peptide , rhodium , organic chemistry , crystal structure , biochemistry , physics , quantum mechanics , magnetic field
The principles of protein structure design, molecular recognition, and supramolecular and combinatorial chemistry have been applied to develop a convergent metal‐ion‐assisted self‐assembly approach that is a very simple and effective method for the de novo design and the construction of topologically predetermined antiparallel β‐sheet structures and self‐assembled catalysts. A new concept of in situ generation of bidentate P‐ligands for transition‐metal catalysis, in which two complementary, monodentate, peptide‐based ligands are brought together by employing peptide secondary structure motif as constructing tool to direct the self‐assembly process, is achieved through formation of stable β‐sheet motifs and subsequent control of selectivity. The supramolecular structures were studied by 1 H, 31 P, and 13 C NMR spectroscopy, ESI mass spectrometry, X‐ray structure ana1ysis, and theoretical calculations. Our initial catalysis results confirm the close relationship between the self‐assembled sheet conformations and the catalytic activity of these metallopeptides in the asymmetric rhodium‐catalyzed hydroformylation. Good catalyst activity and moderate enantioselectivity were observed for the selected combination of catalyst and substrate, but most importantly the concept of this new methodology was successfully proven. This work presents a perspective interface between protein design and supramolecular catalysis for the design of β‐sheet mimetics and screening of libraries of self‐organizing supramolecular catalysts.