5442-00-2Relevant academic research and scientific papers
Titanocenes as Photoredox Catalysts Using Green-Light Irradiation
Flowers, Robert A.,Gans?uer, Andreas,Hilche, Tobias,Oloyede, Ugochinyere N.,Rietdijk, Niels R.,Slak, Daniel,Zhang, Zhenhua
supporting information, p. 9355 - 9359 (2020/04/30)
Irradiation of Cp2TiCl2 with green light leads to electronically excited [Cp2TiCl2]*. This complex constitutes an efficient photoredox catalyst for the reduction of epoxides and for 5-exo cyclizations of suitably unsaturated epoxides. To the best of our knowledge, our system is the first example of a molecular titanium photoredox catalyst.
Ligand-Controlled Direct Hydroformylation of Trisubstituted Olefins
Shin, Taeil,Kim, Hyungsoo,Kim, Sungmin,Lee, Ansoo,Seo, Min-Seob,Choi, Jonghoon,Kim, Hyungjun,Kim, Hyunwoo
supporting information, p. 5789 - 5792 (2019/06/24)
The direct hydroformylation of trisubstituted olefins has been achieved with a combination of a Rh(I) catalyst and a π-acceptor phosphorus (briphos) ligand. A sterically bulky briphos ligand with a large cone angle that forms a 1:1 complex with Rh(I) is found to be reactive for the hydroformylation of trisubstituted olefins. The aldehyde products were obtained with high diastereoselectivity (>99:1) and regioselectivity (49%-81%).
Merging Catalysis in Single Electron Steps with Photoredox Catalysis - Efficient and Sustainable Radical Chemistry
Zhang, Zhenhua,Richrath, Ruben B.,Gans?uer, Andreas
, p. 3208 - 3212 (2019/04/13)
We describe a combination of catalysts that allows the coupling of titanocene(III) catalysis with photoredox catalysis. Oxidation of radical intermediates by a photoredox catalyst opens novel catalytic mechanisms for reductive epoxide ring opening and redox-neutral epoxide radical arylation. In the former case, the requirement of metallic reductants and stoichiometric acidic additives is bypassed.
Cu-Catalyzed Hydroxymethylation of Unactivated Alkyl Iodides with CO To Provide One-Carbon-Extended Alcohols
Zhao, Siling,Mankad, Neal P.
supporting information, p. 5867 - 5870 (2018/04/17)
We have developed a reductive carbonylation method by which unactivated alkyl iodides can be hydroxymethylated to provide one-carbon-extended alcohol products under Cu-catalyzed conditions. The method is tolerant of alkyl β-hydrogen atoms, is robust towards a wide variety of functional groups, and was applied to primary, secondary, and tertiary alkyl iodide substrates. Mechanistic experiments indicate that the transformation proceeds by atom-transfer carbonylation (ATC) of the alkyl iodide followed in tandem by two CuH-mediated reductions in rapid succession. This radical mechanism renders the Cu-catalyzed system complementary to precious-metal-catalyzed reductive carbonylation reactions.
Determination of the Absolute Configuration of β-Chiral Primary Alcohols Using the Competing Enantioselective Conversion Method
Burns, Alexander S.,Wagner, Alexander J.,Fulton, Jennifer L.,Young, Kyle,Zakarian, Armen,Rychnovsky, Scott. D.
supporting information, p. 2953 - 2956 (2017/06/07)
A method for determining the absolute configuration of β-chiral primary alcohols has been developed. Enantioenriched alcohols were acylated in the presence of either enantiomer of the enantioselective acylation catalyst HBTM, and the faster reaction was determined by measuring product conversion using 1H NMR spectroscopic analysis. An empirical mnemonic was developed that correlates the absolute configuration of the alcohol to the faster reacting catalyst. Successful substrates for this method include primary alcohols that bear a "directing group" on the stereogenic center; directing groups include arenes, heteroarenes, enones, and halides.
BIARYL PYRAZOLES AS NRF2 REGULATORS
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Page/Page column 451; 452, (2017/08/01)
The present invention relates to biaryl pyrazole compounds, methods of making them, pharmaceutical compositions containing them and their use as NRF2 regulators.
Highly Active Titanocene Catalysts for Epoxide Hydrosilylation: Synthesis, Theory, Kinetics, EPR Spectroscopy
Henriques, Dina Schwarz G.,Zimmer, Katharina,Klare, Sven,Meyer, Andreas,Rojo-Wiechel, Elena,Bauer, Mirko,Sure, Rebecca,Grimme, Stefan,Schiemann, Olav,Flowers, Robert A.,Gans?uer, Andreas
supporting information, p. 7671 - 7675 (2016/07/07)
A catalytic system for titanocene-catalyzed epoxide hydrosilylation is described. It features a straightforward preparation of titanocene hydrides that leads to a reaction with low catalyst loading, high yields, and high selectivity of radical reduction. The mechanism was studied by a suite of methods, including kinetic studies, EPR spectroscopy, and computational methods. An unusual resting state leads to the observation of an inverse rate order with respect to the epoxide.
NRF2 REGULATORS
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Page/Page column 346; 347, (2017/01/02)
Provided are aryl analogs,pharmaceutical compositions containing them and their use as NRF2 regulators.
Chiral monodentate phosphine ligands for the enantioselective α- And γ-arylation of aldehydes
Franzoni, Ivan,Guénée, Laure,Mazet, Clément
supporting information, p. 4181 - 4190 (2014/06/09)
The synthesis of chiral variants of monodentate trialkyl and dialkylbiaryl phosphine ligands elaborated on the binepine scaffold is described. Their application in the Pd-catalyzed intramolecular asymmetric α-arylation of aldehydes and the intermolecular asymmetric γ-arylation of α,β-unsaturated aldehydes provides a mean of validating the design of these ligands. For the first reaction, excellent reactivities have been obtained while only modest enantioselectivities were measured. Aside from enantioselectivity, the second reaction offers additional challenges associated with intramolecularity and regioselectivity. With the formal chiral trialkyl monodentate phosphine ligands, good yield, high olefin stereocontrol, and perfect γ-selectivity were obtained while the enantioselectivity remained in the low but promising range.
Formic acid: A promising bio-renewable feedstock for fine chemicals
Mura, Manuel G.,Luca, Lidia De,Giacomelli, Giampaolo,Porcheddu, Andrea
supporting information, p. 3180 - 3186 (2013/01/15)
In light of the growing scarcity of petroleum-based raw materials, carbon dioxide (CO2) is becoming increasing attractive as organic carbon source. In this perspective, formic acid (HCOOH) might be an interesting bio-renewable solution to store, transport, and activate carbon dioxide for the synthesis of value-added chemicals. Herein, HCOOH has been successfully used as C1 building block for the synthesis of a library of alcohols via a catalysed oxo-synthesis, under green experimental conditions. Copyright
