Site-Selective Functionalization of (sp3)C-H Bonds Catalyzed by Artificial Metalloenzymes Containing an Iridium-Porphyrin Cofactor

Gu, Yang; Natoli, Sean N.; Liu, Zhennan; Clark, Douglas S.; Hartwig, John F.

doi:10.1002/anie.201907460

Title: Site-Selective Functionalization of (sp³)C-H Bonds Catalyzed by Artificial Metalloenzymes Containing an Iridium-Porphyrin Cofactor

Abstract

The selective functionalization of one C-H bond over others in nearly identical steric and electronic environments can facilitate the construction of complex molecules. We report site-selective functionalizations of C-H bonds, differentiated solely by remote substituents, catalyzed by artificial metalloenzymes (ArMs) that are generated from the combination of an evolvable P450 scaffold and an iridium-porphyrin cofactor. The generated systems catalyze the insertion of carbenes into the C-H bonds of a range of phthalan derivatives containing substituents that render the two methylene positions in each phthalan inequivalent. These reactions occur with site-selectivity ratios of up to 17.8:1 and, in most cases, with pairs of enzyme mutants that preferentially form each of the two constitutional isomers. This study demonstrates the potential of abiotic reactions catalyzed by metalloenzymes to functionalize C-H bonds with site selectivity that is difficult to achieve with small-molecule catalysts.

Authors:

Gu, Yang ^[1]; Natoli, Sean N. ^[1]; Liu, Zhennan ^[1]; Clark, Douglas S. ^[1];

^[1]

Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Publication Date:: Mon Sep 23 00:00:00 EDT 2019

Research Org.:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1633240

Alternate Identifier(s):: OSTI ID: 1558124

Grant/Contract Number:: AC02-05CH11231

Resource Type:: Accepted Manuscript

Journal Name:: Angewandte Chemie (International Edition)

Additional Journal Information:: Journal Name: Angewandte Chemie (International Edition); Journal Volume: 58; Journal Issue: 39; Journal ID: ISSN 1433-7851

Publisher:: Wiley

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Gu, Yang, Natoli, Sean N., Liu, Zhennan, Clark, Douglas S., and Hartwig, John F. Site-Selective Functionalization of (sp3)C-H Bonds Catalyzed by Artificial Metalloenzymes Containing an Iridium-Porphyrin Cofactor.  United States: N. p., 2019. 
Web.  doi:10.1002/anie.201907460.

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                    Gu, Yang, Natoli, Sean N., Liu, Zhennan, Clark, Douglas S., & Hartwig, John F. Site-Selective Functionalization of (sp3)C-H Bonds Catalyzed by Artificial Metalloenzymes Containing an Iridium-Porphyrin Cofactor.  United States.  https://doi.org/10.1002/anie.201907460

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                    Gu, Yang, Natoli, Sean N., Liu, Zhennan, Clark, Douglas S., and Hartwig, John F. Mon .  
"Site-Selective Functionalization of (sp3)C-H Bonds Catalyzed by Artificial Metalloenzymes Containing an Iridium-Porphyrin Cofactor".  United States.  https://doi.org/10.1002/anie.201907460.  https://www.osti.gov/servlets/purl/1633240.

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@article{osti_1633240,

  title        = {Site-Selective Functionalization of (sp3)C-H Bonds Catalyzed by Artificial Metalloenzymes Containing an Iridium-Porphyrin Cofactor},

  author       = {Gu, Yang and Natoli, Sean N. and Liu, Zhennan and Clark, Douglas S. and Hartwig, John F.},

  abstractNote = {The selective functionalization of one C-H bond over others in nearly identical steric and electronic environments can facilitate the construction of complex molecules. We report site-selective functionalizations of C-H bonds, differentiated solely by remote substituents, catalyzed by artificial metalloenzymes (ArMs) that are generated from the combination of an evolvable P450 scaffold and an iridium-porphyrin cofactor. The generated systems catalyze the insertion of carbenes into the C-H bonds of a range of phthalan derivatives containing substituents that render the two methylene positions in each phthalan inequivalent. These reactions occur with site-selectivity ratios of up to 17.8:1 and, in most cases, with pairs of enzyme mutants that preferentially form each of the two constitutional isomers. This study demonstrates the potential of abiotic reactions catalyzed by metalloenzymes to functionalize C-H bonds with site selectivity that is difficult to achieve with small-molecule catalysts.},

  doi          = {10.1002/anie.201907460},

  journal      = {Angewandte Chemie (International Edition)},

  number       = 39,

  volume       = 58,

  place        = {United States},

  year         = {Mon Sep 23 00:00:00 EDT 2019},

  month        = {Mon Sep 23 00:00:00 EDT 2019}

}

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Title: Site-Selective Functionalization of (sp3)C-H Bonds Catalyzed by Artificial Metalloenzymes Containing an Iridium-Porphyrin Cofactor

Abstract

Citation Formats

Ratio of ellipticities between 192 and 208 nm ( R 1 ): An effective electronic circular dichroism parameter for characterization of the helical components of proteins and peptides journal, August 2017

Artificial Metalloenzymes Based on the Biotin–Streptavidin Technology: Challenges and Opportunities journal, August 2016

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Intermolecular Copper-Catalyzed Carbon−Hydrogen Bond Activation via Carbene Insertion journal, February 2002

A survey of Hammett substituent constants and resonance and field parameters journal, March 1991

Selective functionalisation of saturated C–H bonds with metalloporphyrin catalysts journal, January 2011

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Molecular Recognition in the Selective Oxygenation of Saturated C-H Bonds by a Dimanganese Catalyst journal, June 2006

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Gerichtete Evolution: Wie man neue Chemie zum Leben erweckt journal, November 2017

Catalytic Carbene Insertion into C−H Bonds journal, February 2010

Abiological catalysis by artificial haem proteins containing noble metals in place of iron journal, June 2016

Evolving artificial metalloenzymes via random mutagenesis journal, January 2018

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Weak Coordination as a Powerful Means for Developing Broadly Useful C–H Functionalization Reactions journal, December 2011

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Crystallization and preliminary X-ray diffraction analysis of a cytochrome P450 (CYP119) from Sulfolobus solfataricus journal, September 2000

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Directed Evolution of a Cytochrome P450 Carbene Transferase for Selective Functionalization of Cyclic Compounds journal, May 2019

A Site-Selective Dual Anchoring Strategy for Artificial Metalloprotein Design journal, September 2004

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Site-selective and stereoselective functionalization of non-activated tertiary C–H bonds journal, November 2017

Artificial Metalloenzymes Based on the Biotin–Streptavidin Technology: Enzymatic Cascades and Directed Evolution journal, February 2019

Artificial Metalloenzymes Based on the Biotin-Streptavidin Technology: Enzymatic Cascades and Directed Evolution text, January 2019

Title: Site-Selective Functionalization of (sp³)C-H Bonds Catalyzed by Artificial Metalloenzymes Containing an Iridium-Porphyrin Cofactor

Ratio of ellipticities between 192 and 208 nm ( R ₁ ): An effective electronic circular dichroism parameter for characterization of the helical components of proteins and peptides
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Artificial Metalloenzymes Based on the Biotin–Streptavidin Technology: Challenges and Opportunities
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CH Bond Functionalization: Emerging Synthetic Tools for Natural Products and Pharmaceuticals
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Intermolecular Copper-Catalyzed Carbon−Hydrogen Bond Activation via Carbene Insertion
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A survey of Hammett substituent constants and resonance and field parameters
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Selective functionalisation of saturated C–H bonds with metalloporphyrin catalysts
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Design and evolution of enzymes for non-natural chemistry
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Site-selective and stereoselective functionalization of unactivated C–H bonds
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Directed Evolution of Artificial Metalloenzymes: A Universal Means to Tune the Selectivity of Transition Metal Catalysts?
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Molecular Recognition in the Selective Oxygenation of Saturated C-H Bonds by a Dimanganese Catalyst
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Enzymatic assembly of carbon–carbon bonds via iron-catalysed sp3 C–H functionalization
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Noble−Metal Substitution in Hemoproteins: An Emerging Strategy for Abiological Catalysis
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Reactivity Comparison of Primary Aromatic Amines and Thiols in E–H Insertion Reactions with Diazoacetates Catalyzed by Iridium(III) Tetratolylporphyrin
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Gerichtete Evolution: Wie man neue Chemie zum Leben erweckt
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Catalytic Carbene Insertion into C−H Bonds
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Abiological catalysis by artificial haem proteins containing noble metals in place of iron
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Evolving artificial metalloenzymes via random mutagenesis
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Beyond the Second Coordination Sphere: Engineering Dirhodium Artificial Metalloenzymes To Enable Protein Control of Transition Metal Catalysis
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Weak Coordination as a Powerful Means for Developing Broadly Useful C–H Functionalization Reactions
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Directing Group-Controlled Regioselectivity in an Enzymatic C–H Bond Oxygenation
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Funktionalisierung von C-H-Bindungen: neue Synthesemethoden für Naturstoffe und Pharmazeutika
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Complex reactions catalyzed by cytochrome P450 enzymes
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Site-selective enzymatic C‒H amidation for synthesis of diverse lactams
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Directed Evolution: Bringing New Chemistry to Life
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Peptide-Based Catalysts Reach the Outer Sphere through Remote Desymmetrization and Atroposelectivity
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Crystallization and preliminary X-ray diffraction analysis of a cytochrome P450 (CYP119) from Sulfolobus solfataricus
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Engineering of RuMb: Toward a Green Catalyst for Carbene Insertion Reactions
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Directed Evolution of a Cytochrome P450 Carbene Transferase for Selective Functionalization of Cyclic Compounds
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A Site-Selective Dual Anchoring Strategy for Artificial Metalloprotein Design
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Identification of Mechanism-Based Inactivation in P450-Catalyzed Cyclopropanation Facilitates Engineering of Improved Enzymes
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Exploiting and engineering hemoproteins for abiological carbene and nitrene transfer reactions
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Methods for the directed evolution of proteins
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Iridium( iii )-bis(imidazolinyl)phenyl catalysts for enantioselective C–H functionalization with ethyl diazoacetate
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Beyond Iron: Iridium-Containing P450 Enzymes for Selective Cyclopropanations of Structurally Diverse Alkenes
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Understanding and Modulating Metalloenzymes with Unnatural Amino Acids, Non-Native Metal Ions, and Non-Native Metallocofactors
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Metallopeptide catalysts and artificial metalloenzymes containing unnatural amino acids
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An artificial metalloenzyme with the kinetics of native enzymes
journal, October 2016

Site-Selective Carbene-Induced C–H Functionalization Catalyzed by Dirhodium Tetrakis(triarylcyclopropanecarboxylate) Complexes
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Enzymatic hydroxylation of an unactivated methylene C–H bond guided by molecular dynamics simulations
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New Concepts for Increasing the Efficiency in Directed Evolution of Stereoselective Enzymes
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Artificial Metalloenzymes: Reaction Scope and Optimization Strategies
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Catalytic Cyclopropanation by Myoglobin Reconstituted with Iron Porphycene: Acceleration of Catalysis due to Rapid Formation of the Carbene Species
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Metal Substitution Modulates the Reactivity and Extends the Reaction Scope of Myoglobin Carbene Transfer Catalysts
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Chemoselective, Enzymatic C–H Bond Amination Catalyzed by a Cytochrome P450 Containing an Ir(Me)-PIX Cofactor
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Innate and Guided C–H Functionalization Logic
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Evolution of C–H Bond Functionalization from Methane to Methodology
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Preparation of Artificial Metalloenzymes by Insertion of Chromium(III) Schiff Base Complexes into Apomyoglobin Mutants
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Site-selective and stereoselective functionalization of non-activated tertiary C–H bonds
journal, November 2017

Artificial Metalloenzymes Based on the Biotin–Streptavidin Technology: Enzymatic Cascades and Directed Evolution
journal, February 2019

Artificial Metalloenzymes Based on the Biotin-Streptavidin Technology: Enzymatic Cascades and Directed Evolution
text, January 2019