Accounts of Chemical Research, volume 53, issue 10, pages 2456-2471

Light-Activated Olefin Metathesis: Catalyst Development, Synthesis, and Applications

Or Eivgi ¹

Ravindra S Phatake ¹

Noy B Nechmad ¹

N Gabriel Lemcoff ^{1, 2}

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Department of Chemistry, Ben-Gurion University of the Negev, Beer-Sheva 84105, Israel |

Ilse Katz Institute for Nanoscale Science and Technology, Ben-Gurion University of the Negev, Beer-Sheva 84105, Israel |

Publication type: Journal Article

Publication date: 2020-09-29

American Chemical Society (ACS)

Journal: Accounts of Chemical Research

Quartile SCImago

Quartile WOS

Impact factor: 18.3

ISSN: 00014842, 15204898

DOI: 10.1021/acs.accounts.0c00495

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General Chemistry

General Medicine

Abstract

The most important means for tuning and improving a catalyst's properties is the delicate exchange of the ligand shell around the central metal atom. Perhaps for no other organometallic-catalyzed reaction is this statement more valid than for ruthenium-based olefin metathesis. Indeed, even the simple exchange of an oxygen atom for a sulfur atom in a chelated ruthenium benzylidene about a decade ago resulted in the development of extremely stable, photoactive catalysts. This Account presents our perspective on the development of dormant olefin metathesis catalysts that can be activated by external stimuli and, more specifically, the use of light as an attractive inducing agent.The insight gained from a deeper understanding of the properties of cis-dichlororuthenium benzylidenes opened the doorway for the systematic development of new and efficient light-activated olefin metathesis catalysts and catalytic chromatic-orthogonal synthetic schemes. Following this, ways to disrupt the ligand-to-metal bond to accelerate the isomerization process that produced the active precatalyst were actively pursued. Thus, we summarize herein the original thermal activation experiments and how they brought about the discoveries of photoactivation in the sulfur-chelated benzylidene family of catalysts. The specific wavelengths of light that were used to dissociate the sulfur-ruthenium bond allowed us to develop noncommutative catalytic chromatic-orthogonal processes and to combine other photochemical reactions with photoinduced olefin metathesis, including using external light-absorbing molecules as sunscreens to achieve novel selectivities. Alteration of the ligand sphere, including modifications of the N-heterocyclic carbene (NHC) ligand and the introduction of cyclic alkyl amino carbene (CAAC) ligands, produced more efficient light-induced activity and special chemical selectivity. The use of electron-rich sulfoxides and, more prominently, phosphites as the agents that induce latency widened the spectrum of light-induced olefin metathesis reactions even further by expanding the colors of light that may now be used to activate the catalysts, which can be used in applications such as stereolithography and 3D printing of tough metathesis-derived polymers.

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Journal of Physical Chemistry A	Journal of Physical Chemistry A, 1, 2.27% Journal of Physical Chemistry A 1 publication, 2.27%
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American Chemical Society (ACS)	American Chemical Society (ACS), 18, 40.91% American Chemical Society (ACS) 18 publications, 40.91%
Wiley	Wiley, 9, 20.45% Wiley 9 publications, 20.45%
Elsevier	Elsevier, 5, 11.36% Elsevier 5 publications, 11.36%
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Springer Nature	Springer Nature, 2, 4.55% Springer Nature 2 publications, 4.55%
Multidisciplinary Digital Publishing Institute (MDPI)	Multidisciplinary Digital Publishing Institute (MDPI), 1, 2.27% Multidisciplinary Digital Publishing Institute (MDPI) 1 publication, 2.27%
American Association for the Advancement of Science (AAAS)	American Association for the Advancement of Science (AAAS), 1, 2.27% American Association for the Advancement of Science (AAAS) 1 publication, 2.27%
Thieme	Thieme, 1, 2.27% Thieme 1 publication, 2.27%
International Union of Crystallography (IUCr)	International Union of Crystallography (IUCr), 1, 2.27% International Union of Crystallography (IUCr) 1 publication, 2.27%
Autonomous Non-profit Organization Editorial Board of the journal Uspekhi Khimii	Autonomous Non-profit Organization Editorial Board of the journal Uspekhi Khimii, 1, 2.27% Autonomous Non-profit Organization Editorial Board of the journal Uspekhi Khimii 1 publication, 2.27%
	2 4 6 8 10 12 14 16 18

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Eivgi O. et al. Light-Activated Olefin Metathesis: Catalyst Development, Synthesis, and Applications // Accounts of Chemical Research. 2020. Vol. 53. No. 10. pp. 2456-2471.

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Eivgi O., Phatake R. S., Nechmad N. B., Lemcoff N. G. Light-Activated Olefin Metathesis: Catalyst Development, Synthesis, and Applications // Accounts of Chemical Research. 2020. Vol. 53. No. 10. pp. 2456-2471.

RIS |

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TY - JOUR

DO - 10.1021/acs.accounts.0c00495

UR - https://doi.org/10.1021/acs.accounts.0c00495

TI - Light-Activated Olefin Metathesis: Catalyst Development, Synthesis, and Applications

T2 - Accounts of Chemical Research

AU - Eivgi, Or

AU - Phatake, Ravindra S

AU - Lemcoff, N Gabriel

AU - Nechmad, Noy B

PY - 2020

DA - 2020/09/29 00:00:00

PB - American Chemical Society (ACS)

SP - 2456-2471

IS - 10

VL - 53

SN - 0001-4842

SN - 1520-4898

ER -

BibTex |

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BibTex Copy

@article{2020_Eivgi,

author = {Or Eivgi and Ravindra S Phatake and N Gabriel Lemcoff and Noy B Nechmad},

title = {Light-Activated Olefin Metathesis: Catalyst Development, Synthesis, and Applications},

journal = {Accounts of Chemical Research},

year = {2020},

volume = {53},

publisher = {American Chemical Society (ACS)},

month = {sep},

url = {https://doi.org/10.1021/acs.accounts.0c00495},

number = {10},

pages = {2456--2471},

doi = {10.1021/acs.accounts.0c00495}

}

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Eivgi, Or, et al. “Light-Activated Olefin Metathesis: Catalyst Development, Synthesis, and Applications.” Accounts of Chemical Research, vol. 53, no. 10, Sep. 2020, pp. 2456-2471. https://doi.org/10.1021/acs.accounts.0c00495.

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Publisher

American Chemical Society (ACS)

Journal

Accounts of Chemical Research

Quartile SCImago

Quartile WOS

Impact factor

18.3

ISSN

00014842 (Print)
15204898 (Electronic)