Supramolecular bidentate ligands by metal-directed in situ formation of antiparallel beta-sheet structures and application in asymmetric catalysis

Andy C. Laungani; John M. Slattery; Ingo Krossing; Bernhard Breit

doi:10.1002/chem.200800359

Supramolecular bidentate ligands by metal-directed in situ formation of antiparallel beta-sheet structures and application in asymmetric catalysis

Andy C. Laungani, John M. Slattery, Ingo Krossing, Bernhard Breit

Chemistry

Research output: Contribution to journal › Literature review › peer-review

Abstract

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 beta-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 beta-sheet motifs and subsequent control of selectivity. The supramolecular structures were studied by H-1, P-31, and C-13 NMR spectroscopy, ESI mass spectrometry, X-ray structure analysis, 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 beta-sheet mimetics and screening of libraries of self-organizing supramolecular catalysts.

Original language	English
Pages (from-to)	4488-4502
Number of pages	15
Journal	Chemistry - A European Journal
Volume	14
Issue number	15
DOIs	https://doi.org/10.1002/chem.200800359
Publication status	Published - 2008

Keywords

asymmetric catalysis
beta sheets
combinatorial chemistry
metallopeptides
self-assembly
supramolecular chemistry
COMBINATORIAL HOMOGENEOUS CATALYSIS
NUCLEAR-MAGNETIC-RESONANCE
PEPTIDE-BASED CATALYSTS
SOLID-PHASE SYNTHESIS
DE-NOVO DESIGN
PROTON PROTON DISTANCES
UNNATURAL AMINO-ACID
BASE-PAIR MODEL
HYDROGEN-BOND
CONJUGATE ADDITIONS

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title = "Supramolecular bidentate ligands by metal-directed in situ formation of antiparallel beta-sheet structures and application in asymmetric catalysis",

abstract = "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 beta-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 beta-sheet motifs and subsequent control of selectivity. The supramolecular structures were studied by H-1, P-31, and C-13 NMR spectroscopy, ESI mass spectrometry, X-ray structure analysis, 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 beta-sheet mimetics and screening of libraries of self-organizing supramolecular catalysts.",

keywords = "asymmetric catalysis, beta sheets, combinatorial chemistry, metallopeptides, self-assembly, supramolecular chemistry, COMBINATORIAL HOMOGENEOUS CATALYSIS, NUCLEAR-MAGNETIC-RESONANCE, PEPTIDE-BASED CATALYSTS, SOLID-PHASE SYNTHESIS, DE-NOVO DESIGN, PROTON PROTON DISTANCES, UNNATURAL AMINO-ACID, BASE-PAIR MODEL, HYDROGEN-BOND, CONJUGATE ADDITIONS",

author = "Laungani, {Andy C.} and Slattery, {John M.} and Ingo Krossing and Bernhard Breit",

year = "2008",

doi = "10.1002/chem.200800359",

language = "English",

volume = "14",

pages = "4488--4502",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "Wiley-Blackwell",

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T1 - Supramolecular bidentate ligands by metal-directed in situ formation of antiparallel beta-sheet structures and application in asymmetric catalysis

AU - Laungani, Andy C.

AU - Slattery, John M.

AU - Krossing, Ingo

AU - Breit, Bernhard

PY - 2008

Y1 - 2008

N2 - 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 beta-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 beta-sheet motifs and subsequent control of selectivity. The supramolecular structures were studied by H-1, P-31, and C-13 NMR spectroscopy, ESI mass spectrometry, X-ray structure analysis, 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 beta-sheet mimetics and screening of libraries of self-organizing supramolecular catalysts.

AB - 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 beta-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 beta-sheet motifs and subsequent control of selectivity. The supramolecular structures were studied by H-1, P-31, and C-13 NMR spectroscopy, ESI mass spectrometry, X-ray structure analysis, 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 beta-sheet mimetics and screening of libraries of self-organizing supramolecular catalysts.

KW - asymmetric catalysis

KW - beta sheets

KW - combinatorial chemistry

KW - metallopeptides

KW - self-assembly

KW - supramolecular chemistry

KW - COMBINATORIAL HOMOGENEOUS CATALYSIS

KW - NUCLEAR-MAGNETIC-RESONANCE

KW - PEPTIDE-BASED CATALYSTS

KW - SOLID-PHASE SYNTHESIS

KW - DE-NOVO DESIGN

KW - PROTON PROTON DISTANCES

KW - UNNATURAL AMINO-ACID

KW - BASE-PAIR MODEL

KW - HYDROGEN-BOND

KW - CONJUGATE ADDITIONS

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U2 - 10.1002/chem.200800359

DO - 10.1002/chem.200800359

M3 - Literature review

SN - 0947-6539

VL - 14

SP - 4488

EP - 4502

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 15

ER -

Supramolecular bidentate ligands by metal-directed in situ formation of antiparallel beta-sheet structures and application in asymmetric catalysis

Abstract

Keywords

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