Compositions and methods for visible-light-controlled ruthenium-catalyzed olefin metathesis
Inventors
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Assignees
Columbia University in the City of New York
Member
Columbia UniversityColumbia University is a leading Ivy League research university in New York City, founded in 1754. It comprises undergraduate and graduate programs across 17+ schools, a world-renowned medical center, and nearly 200 research centers and institutes. The Global Alliance for Preventing Pandemics (GAPP) in the Mailman School of Public Health is dedicated to capacity building through workforce development and democratization of technology to provide public health professionals in the Global South every opportunity to independently identify and contain pathogen outbreaks. GAPP focuses on sharing sustainable technologies and best technical practices involving sequencing, serological, and rapid diagnostics tools so public health teams are poised to achieve their very different goals addressing their varied and evolving needs. GAPP works closely with the US CDC, NIAID, WHO, GOARN, foundations dedicated to global health and medical equity, and local and regional ministries of health and education to address human health, and the ministries of livestock and fisheries to help address food security while fostering a culture of the open sharing of data.
Columbia University is a leading Ivy League research university in New York City, founded in 1754. It comprises undergraduate and graduate programs across 17+ schools, a world-renowned medical center, and nearly 200 research centers and institutes. The Global Alliance for Preventing Pandemics (GAPP) in the Mailman School of Public Health is dedicated to capacity building through workforce development and democratization of technology to provide public health professionals in the Global South every opportunity to independently identify and contain pathogen outbreaks. GAPP focuses on sharing sustainable technologies and best technical practices involving sequencing, serological, and rapid diagnostics tools so public health teams are poised to achieve their very different goals addressing their varied and evolving needs. GAPP works closely with the US CDC, NIAID, WHO, GOARN, foundations dedicated to global health and medical equity, and local and regional ministries of health and education to address human health, and the ministries of livestock and fisheries to help address food security while fostering a culture of the open sharing of data.
Publication Number
US-12377407-B2
Publication Date
2025-08-05
Expiration Date
Abstract
The present disclosure provides compositions and methods for metathesizing a first alkenyl or alkynyl group with a second alkenyl or alkynyl group, the composition comprising a ruthenium metathesis catalyst and a photoredox catalyst that is activated by visible light.
Core Innovation
The invention provides compositions and methods for metathesizing a first alkenyl or alkynyl group with a second alkenyl or alkynyl group, the composition comprising a ruthenium metathesis catalyst and a photoredox catalyst that is activated by visible light. The metathesis described herein is performed using a ruthenium metathesis catalyst and a photoredox catalyst that is activated by visible light, where "visible light" refers to light that has a wavelength of about 350 nm to about 750 nm. In some embodiments the disclosure provides the use of a latent ruthenium metathesis catalyst bearing two poorly dissociable carbene ligands that is not active for metathesis at ambient temperature without external activation.
The disclosure provides methods of spatially controlling a metathesis comprising forming a mixture of a ruthenium metathesis catalyst, a photoredox catalyst, and one or more compounds susceptible to metathesis; and applying visible light to one or more regions of the mixture so as to give rise to one or more metathesized regions and one or more unmetathesized regions. The visible light can be applied using a high resolution light source or by covering at least one unmetathesized region with a photomask, and the substrate can be functionalized with the one or more compounds susceptible to metathesis. The methods encompass ring-closing metathesis, cross-metathesis, ring-opening metathesis polymerization, and photolithographic olefin metathesis polymerization as metathesis types.
The disclosure describes activation by the photoredox catalyst where energy or electron transfer from/to the excited state of the photocatalyst induces ligand dissociation from the latent metathesis catalyst, generating the active species that promotes ROMP and related reactions; turning the light off leads to re-coordination of the carbene ligand onto the ruthenium catalyst and is thought to shut down metathesis. The disclosure describes that photoredox catalysts that are highly oxidizing contribute to the ease of metathesis and provides examples of photoredox catalysts and bis(NHC)-ruthenium complexes. As a result, the methods are presented as permitting control of initiation and termination of ROMP and enabling temporal and spatial control over product formation.
Claims Coverage
Two independent claims were identified in the patent.
Composition for metathesizing alkenyl or alkynyl groups
A composition for metathesizing a first alkenyl or alkynyl group with a second alkenyl or alkynyl group, comprising a ruthenium metathesis catalyst that is (SIMes)2RuCl2CHPh or (IMes)2RuCl2CHPh.
Visible-light chemical metathesis method
A method for chemical metathesis comprising applying visible light to the composition of claim 1 in the presence of a ruthenium metathesis catalyst and a photoredox catalyst that is activated by visible light.
The independent claims cover (1) compositions for metathesizing alkenyl/alkynyl groups that comprise specific bis(NHC)-ruthenium catalysts and (2) a method of performing chemical metathesis by applying visible light to such a composition in the presence of a photoredox catalyst activated by visible light.
Stated Advantages
Minimal reagent requirements.
Ability to use visible light, reducing or eliminating the need for more complicated illumination sources.
Ability to utilize a broad range of starting materials to arrive at a broad range of products.
Ability to exert both temporal and spatial control over product formation, including control of initiation and termination of ROMP and control over polymer chain length, average molecular weight, and dispersity.
Documented Applications
Polymer production.
Polymer patterning.
Photolithography, including photolithographic olefin metathesis polymerization (PLOMP).
3-D printing.
Ring-opening metathesis polymerization (ROMP) and related polymer fabrication methods.
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