A red-light-activated phthalocyanine ruthenium complex has been designed as a catalyst for the bifunctionalization of styrene derivatives. The combination of a trifluoromethylation agent resistant to nucleophiles and various nucleophiles facilitates the concurrent incorporation of a trifluoromethyl group and various functional groups onto the double bond of the substrate. This reaction demonstrates the utility of mild, low-energy, and highly transmissive long-wavelength light for intricate molecular transformations in a one-pot procedure.
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http://dx.doi.org/10.1021/acs.joc.4c00889 | DOI Listing |
J Org Chem
June 2024
NanoMaterials Research Institute, Kanazawa University, Kakuma-machi, Kanazawa 920-1192, Japan.
A red-light-activated phthalocyanine ruthenium complex has been designed as a catalyst for the bifunctionalization of styrene derivatives. The combination of a trifluoromethylation agent resistant to nucleophiles and various nucleophiles facilitates the concurrent incorporation of a trifluoromethyl group and various functional groups onto the double bond of the substrate. This reaction demonstrates the utility of mild, low-energy, and highly transmissive long-wavelength light for intricate molecular transformations in a one-pot procedure.
View Article and Find Full Text PDFOrg Biomol Chem
September 2023
School of Biotechnology and Health Sciences, Wuyi University, Jiangmen 529020, China.
By opening the ring of a benzothiazole salt, we provide a sulfur source for the bifunctional reaction of styrene. The ring-opening-recombination reaction of the benzothiazole salt simultaneously constructs new C-S, C-O, and CO bonds after C-S bond breaking. The reaction proceeds in green solvents, requires no transition metal catalyst, and is compatible with many functional groups.
View Article and Find Full Text PDFOrg Lett
March 2021
Chinese Academy of Sciences Key Laboratory of Receptor Research, Shanghai Institute of Materia Medica, University of Chinese Academy of Sciences, Shanghai 201203, China.
Mizoroki-Heck reaction of unstrained aryl ketone with acrylate/styrene is accomplished via palladium-catalyzed ligand-promoted C-C bond cleavage. Various (hetero)aryl ketones are compatible in the reaction, affording the alkene product in good to excellent yields. Further applications in the late-stage olefination of some drugs, natural products, and fragrance-derived aryl ketones demonstrate the synthetic utility of this protocol.
View Article and Find Full Text PDFChemistry
September 2020
State Key Laboratory of Fine Chemicals, Department of Polymer Science and Engineering, Liaoning Key Laboratory of Polymer Science and Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian, Liaoning, 116024, China.
Liquid crystalline block copolymers (LCBCPs) are promising for developing functional materials owing to an assembly of better functionalities. Taking advantage of differences in reactivity between alkynyl and vinyl over temperature during hydrosilylation, a series of LCBCPs with modular functionalization of the block copolymers (BCPs) are reported by independently and site-selectively attaching azobenzene moieties containing alkynyl (LC ) and Si-H (LC ) terminals into well-designed poly(styrene)-block-polybutadienes (PS-b-PBs) and poly(4-vinylphenyldimethylsilane)-block-polybutadienes (PVPDMS-b-PBs) produced from living anionic polymerization (LAP). By the principle of modular functionalization, it is demonstrated that mono-functionalized (PVPDMS-g-LC )-b-PB and PS-b-(PB-g-LC ) not only maintain independence but also have cooperative contributions to bi-functionalized (PVPDMS-g-LC )-b-(PB-g-LC ) in terms of mesomorphic performances and microphase separation, which is evident from differential scanning calorimetry (DSC) and polarized optical morphologies (POM) and identified by powder X-ray diffractions.
View Article and Find Full Text PDFPolymers (Basel)
February 2020
Department of Materials and Optoelectronic Science, Center of Crystal Research, National Sun Yat-Sen University, Kaohsiung 80424, Taiwan.
In this study, we synthesized two main chain-type block copolymers featuring hydrogen bond donor and acceptor segments through atom transfer radical polymerization (ATRP) using a bifunctionalized polyhedral oligomeric silsesquioxane (POSS) nanoparticle as the initiator. Hydrosilylation of vinylbenzyl chloride at the two corners of a double-decker silsesquioxane (DDSQ) provided the bifunctionalized benzyl chloride initiator VBC-DDSQ-VBC, which we applied as a platform to prepare a main chain-type polystyrene homopolymer (PS-DDSQ-PS), the diblock copolymer poly(styrene--4-vinylpyridine) (P4VP-b-PS-DDSQ-PS-b-P4VP), and the diblock copolymer poly(styrene---butoxystyrene) (PtBuOS-b-PS-DDSQ-PS-b-PtBuOS) through sequential ATRP. Selective hydrolysis of the -butoxyl units of PtBuOS-b-PS-DDSQ-PS-b-PtBuOS yielded the strongly hydrogen bonding diblock copolymer poly (styrene--vinylphenol) (PVPh-b-PS-DDSQ-PS-b-PVPh).
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