70882-48-3Relevant academic research and scientific papers
A domino copper-catalyzed C-O coupling-Claisen rearrangement process
Nordmann, Gero,Buchwald, Stephen L.
, p. 4978 - 4979 (2003)
A practical method for the diastereoselective generation of two adjacent quarternary stereocenters by combining a copper-catalyzed C-O coupling reaction with a subsequent Claisen rearrangement in a one-pot domino process is described. Furthermore, an experimentally simple method for the stereoselective synthesis of a variety of different types of vinyl ethers is delineated using the same catalyst system. Copyright
Photo-triggered hydrogen atom transfer from an iridium hydride complex to unactivated olefins
Guo, Xingwei,Pfund, Bj?rn,Schreier, Mirjam R.,Wenger, Oliver S.
, p. 8582 - 8594 (2020/09/07)
Many photoactive metal complexes can act as electron donors or acceptors upon photoexcitation, but hydrogen atom transfer (HAT) reactivity is rare. We discovered that a typical representative of a widely used class of iridium hydride complexes acts as an H-atom donor to unactivated olefins upon irradiation at 470 nm in the presence of tertiary alkyl amines as sacrificial electron and proton sources. The catalytic hydrogenation of simple olefins served as a test ground to establish this new photo-reactivity of iridium hydrides. Substrates that are very difficult to activate by photoinduced electron transfer were readily hydrogenated, and structure-reactivity relationships established with 12 different olefins are in line with typical HAT reactivity, reflecting the relative stabilities of radical intermediates formed by HAT. Radical clock, H/D isotope labeling, and transient absorption experiments provide further mechanistic insight and corroborate the interpretation of the overall reactivity in terms of photo-triggered hydrogen atom transfer (photo-HAT). The catalytically active species is identified as an Ir(ii) hydride with an IrII-H bond dissociation free energy around 44 kcal mol-1, which is formed after reductive 3MLCT excited-state quenching of the corresponding Ir(iii) hydride, i.e. the actual HAT step occurs on the ground-state potential energy surface. The photo-HAT reactivity presented here represents a conceptually novel approach to photocatalysis with metal complexes, which is fundamentally different from the many prior studies relying on photoinduced electron transfer. This journal is
One simple Ir/hydrosilane catalytic system for chemoselective isomerization of 2-substituted allylic ethers
Gao, Weiwei,Zhang, Xueyan,Xie, Xingze,Ding, Shengtao
supporting information, p. 2012 - 2015 (2020/02/22)
Here, we describe one simple Ir/hydrosilane catalytic system for chemoselective isomerization of 2-substituted allylic ethers. This facile strategy shows high efficiency towards a variety of substrates, including derivatives from bioactive molecules. The
Synthesis of Piperidine Derivatives by Rhodium- Catalyzed Tandem Reaction of N-Sulfonyl-1,2,3-Triazole and Vinyl Ether
Yu, Sisi,An, Yuehui,Wang, Wenlin,Xu, Ze-Feng,Li, Chuan-Ying
supporting information, p. 2125 - 2130 (2018/04/17)
A chemoselective tandem reaction of 4-acyloxymethylene-1-sulfonyl-1,2,3-triazole and vinyl ether was reported, producing polysubstituted piperidine derivatives in up to 96% yield. The key intermediate N-sulfonyl 1-azadiene generated by migration of the OAc group to the α-imino rhodium carbene was isolated and a plausible mechanism was proposed. Several related ring systems were constructed from the highly functionalized products. (Figure presented.).
Simple, chemoselective, catalytic olefin isomerization
Crossley, Steven W. M.,Barabé, Francis,Shenvi, Ryan A.
supporting information, p. 16788 - 16791 (2015/01/09)
Catalytic amounts of Co(SaltBu,tBu)Cl and organosilane irreversibly isomerize terminal alkenes by one position. The same catalysts effect cycloisomerization of dienes and retrocycloisomerization of strained rings. Strong Lewis bases like amines and imidazoles, and labile functionalities like epoxides, are tolerated.
Encapsulated molecular catalysts in polysiloxane gels: Ruthenium cluster-catalyzed isomerization of alkenes
Motoyama, Yukihiro,Abe, Motonori,Kamo, Kazuyuki,Kosako, Yusuke,Nagashima, Hideo
supporting information; experimental part, p. 5321 - 5323 (2009/03/11)
Novel ruthenium-encapsulating polysiloxane gels are prepared by treatment of polymethylhydrosiloxane with diols in the presence of (μ3, η2,η3,η5-acenaphthylene)Ru 3(CO)7, and act as reusable catalysts in the isomerization of alkenes without leakage of the catalyst species. The Royal Society of Chemistry.
Copper-catalyzed formation of carbon-heteroatom and carbon-carbon bonds
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, (2015/03/06)
The present invention relates to copper-catalyzed carbon-heteroatom and carbon-carbon bond-forming methods. In certain embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-nitrogen bond between the nitrogen atom of an amide or amine moiety and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In additional embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-nitrogen bond between a nitrogen atom of an acyl hydrazine and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In other embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-nitrogen bond between the nitrogen atom of a nitrogen-containing heteroaromatic, e.g., indole, pyrazole, and indazole, and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In certain embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-oxygen bond between the oxygen atom of an alcohol and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. The present invention also relates to copper-catalyzed methods of forming a carbon-carbon bond between a reactant comprising a nucleophilic carbon atom, e.g., an enolate or malonate anion, and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. Importantly, all the methods of the present invention are relatively inexpensive to practice due to the low cost of the copper comprised by the catalysts.
Intra- and intermolecular 1,3-dipolar cycloaddition of sugar ketonitrones with mono-, di-, and trisubstituted dipolarophiles
Torrente, Susana,Noya, Beatriz,Branchadell, Vicenc,Alonso, Ricardo
, p. 4772 - 4783 (2007/10/03)
The 1,3-dipolar cycloaddition of sugar ketonitrones is a useful synthetic procedure to build up nitrogenated quaternary centers in terms of scope (substrate, dipolarophile, inter- and intramolecular versions), yield, and regio- and stereoselectivity. The
SYNTHESIS OF 2-METHYLPROPENYL SULFIDES AND THEIR OXYGEN AND NITROGEN ANALOGS
Turchaninova, L.P.,Shipov, A.G.,Korchevin, N.A.,Deryagina, E.N.,Baukov, Yu.I.,Voronkov, M.G.
, p. 1889 - 1892 (2007/10/02)
Conditions were developed for the convinient preparative synthesis of 2-methylpropenyl sulfides and their oxygen and nitrogen analogs on the basis of reactions of thiols, alcohols, and lactams with isobutyraldehyde in excess of chlorotrimethylsilane.By-pr
