64145-51-3Relevant articles and documents
A readily prepared neutral heterobimetallic titanium(IV)-rhodium(I) catalyst for intramolecular hydroacylation
Morgan, John P.,Kundu, Kousik,Doyle, Michael P.
, p. 3307 - 3309 (2005)
The combination of HOCMe2CH2PPh2, Ti(OzPr)4, and [Rh(cod)Cl]2 (3:1:1) in either benzene or dichloromethane produces a discrete species (tentatively formulated as complex 14) that is an active catalyst for intramolecular hydroacylation reactions of 3-substituted pentenals. The Royal Society of Chemistry 2005.
Enantioselective Hydrogenation of Endocyclic Enones: the Solution to a Historical Problem?
Lang, Qiwei,Yang, Huaxin,Gu, Guoxian,Feng, Qiang,Wen, Jialin,Zhang, Xumu
supporting information, p. 933 - 936 (2021/03/03)
The enantioselective hydrogenation of endocyclic enones has been a historical problem for homogeneous catalysis. We herein report an efficient method to reduce endocyclic enones with molecular hydrogen. Catalyzed by a rhodium/Zhaophos complex, a variety of enones with five-, six- or seven-member ring were hydrogenated with high enantioselectivity (92%—99% ee). Excellent chemo- and enantioselectivity demonstrated this method was successfully applied in the enantioselective hydrogenation of citral to produce enantio-enriched citronellal.
Asymmetric Synthesis of Chiral Bicyclo[2.2.1]hepta-2,5-diene Ligands through Rhodium-Catalyzed Asymmetric Arylative Bis-cyclization of a 1,6-Enyne
Chen, Chen,Hayashi, Tamio,Meng, He,Ming, Jialin,Sun, Chao,Wei, Haili
supporting information, p. 6311 - 6315 (2021/09/02)
A series of novel chiral diene ligands (1R,4S)-L1, which are based on the bicyclo[2.2.1]heptadiene skeleton and are substituted with methyl and an ester group at the bridgehead carbons, were synthesized through rhodium-catalyzed asymmetric arylative bis-c
Chiral N-aryl tert-butanesulfinamide-olefin ligands for rhodium-catalyzed asymmetric 1,4-addition of aryl boronic acids to cyclic enones
Yuan, Shuai,Zeng, Qingle,Wang, Jiajun,Zhou, Lihong
supporting information, p. 32 - 42 (2021/02/09)
Chiral N-aryl sulfinamide-olefins which are readily synthesized via C-N coupling and nucleophilic substitution have been used as chiral ligands, which demonstrate moderate to excellent asymmetric catalytic performance in the rhodium-catalyzed asymmetric 1
Deciphering Reactivity and Selectivity Patterns in Aliphatic C-H Bond Oxygenation of Cyclopentane and Cyclohexane Derivatives
Martin, Teo,Galeotti, Marco,Salamone, Michela,Liu, Fengjiao,Yu, Yanmin,Duan, Meng,Houk,Bietti, Massimo
supporting information, p. 9925 - 9937 (2021/06/30)
A kinetic, product, and computational study on the reactions of the cumyloxyl radical with monosubstituted cyclopentanes and cyclohexanes has been carried out. HAT rates, site-selectivities for C-H bond oxidation, and DFT computations provide quantitative information and theoretical models to explain the observed patterns. Cyclopentanes functionalize predominantly at C-1, and tertiary C-H bond activation barriers decrease on going from methyl- and tert-butylcyclopentane to phenylcyclopentane, in line with the computed C-H BDEs. With cyclohexanes, the relative importance of HAT from C-1 decreases on going from methyl- and phenylcyclohexane to ethyl-, isopropyl-, and tert-butylcyclohexane. Deactivation is also observed at C-2 with site-selectivity that progressively shifts to C-3 and C-4 with increasing substituent steric bulk. The site-selectivities observed in the corresponding oxidations promoted by ethyl(trifluoromethyl)dioxirane support this mechanistic picture. Comparison of these results with those obtained previously for C-H bond azidation and functionalizations promoted by the PINO radical of phenyl and tert-butylcyclohexane, together with new calculations, provides a mechanistic framework for understanding C-H bond functionalization of cycloalkanes. The nature of the HAT reagent, C-H bond strengths, and torsional effects are important determinants of site-selectivity, with the latter effects that play a major role in the reactions of oxygen-centered HAT reagents with monosubstituted cyclohexanes.
BCL-2 INHIBITOR
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Paragraph 0582-0584, (2021/10/22)
Disclosed herein is a compound of Formula (I) for inhibiting both Bcl-2 wild type and mutated Bcl-2, in particular, Bcl-2 G101V and D103Y, and a method of using the compound disclosed herein for treating dysregulated apoptotic diseases.
Experimental and Theoretical Study on the Role of Monomeric vs Dimeric Rhodium Oxazolidinone Norbornadiene Complexes in Catalytic Asymmetric 1,2- And 1,4-Additions
Abitaev, Karina,Alvarez-Barcia, Sonia,Baro, Angelika,Bauer, Alina,Bauer, Matthias,Estes, Deven P.,Fischer, Felix Richard,Frey, Wolfgang,Gugeler, Katrin,K?stner, Johannes,Kirchhof, Manuel,Laschat, Sabine,Nowakowski, Michal,Plietker, Bernd,Qawasmi, Yaseen,Ringenberg, Mark R.,Schnierle, Marc,Sottmann, Thomas
supporting information, p. 3131 - 3145 (2020/10/02)
The influence of nuclearity and charge of chiral Rh diene complexes on the activity and enantioselectivity in catalytic asymmetric 1,2-additions of organoboron reagents to N-tosylimines and 1,4-additions to enones was investigated. For this purpose, catio
The Silicon-Hydrogen Exchange Reaction: A Catalytic σ-Bond Metathesis Approach to the Enantioselective Synthesis of Enol Silanes
Zhou, Hui,Bae, Han Yong,Leutzsch, Markus,Kennemur, Jennifer L.,Bécart, Diane,List, Benjamin
supporting information, p. 13695 - 13700 (2020/08/24)
The use of chiral enol silanes in fundamental transformations such as Mukaiyama aldol, Michael, and Mannich reactions as well as Saegusa-Ito dehydrogenations has enabled the chemical synthesis of enantiopure natural products and valuable pharmaceuticals. However, accessing these intermediates in high enantiopurity has generally required the use of either stoichiometric chiral precursors or stoichiometric chiral reagents. We now describe a catalytic approach in which strongly acidic and confined imidodiphosphorimidates (IDPi) catalyze highly enantioselective interconversions of ketones and enol silanes. These "silicon-hydrogen exchange reactions"enable access to enantiopure enol silanes via tautomerizing σ-bond metatheses, either in a deprotosilylative desymmetrization of ketones with allyl silanes as the silicon source or in a protodesilylative kinetic resolution of racemic enol silanes with a carboxylic acid as the silyl acceptor.
Tricyclic Sulfoxide-Alkene Hybrid Ligands for Chiral Rh(I) Complexes: The "Matched" Diastereomer Catalyzes Asymmetric C-C Bond Formations
Nikol, Alexander,Zhang, Ziyun,Chelouan, Ahmed,Falivene, Laura,Cavallo, Luigi,Herrera, Alberto,Heinemann, Frank W.,Escalona, Ana,Frie?, Sibylle,Grasruck, Alexander,Dorta, Romano
supporting information, p. 1348 - 1359 (2020/03/30)
Deprotonation of phenyldibenzo[b,f]tropylidene (8) with LDA/t-BuOK followed by quenching with either diastereomer of inexpensive glucose-based t-Bu-sulfinate (R)- or (S)-11 affords a sulfoxide-alkene hybrid ligand as the diastereomeric pairs (SS,SC)-9/(SS,RC)-10 and (RS,RC)-9/(RS,SC)-10, respectively, which via chromatographic/recrystallization may be separated into the four isomers. The optically pure diastereomeric ligands (SS,SC)-9 and (SS,RC)-10 react with [RhCl(coe)2]2 to form the dinuclear complexes (RS,SC)-11 and (RS,RC)-12, respectively, in which the bidentate ligands coordinate the metal centers through the sulfur and alkene donor functions. These complexes catalyze the conjugate addition of arylboronic acids to cyclic Michael acceptors with enantioselectivities of up to 99% ee. DFT calculations show the preponderant influence of planar chirality of the ligand alkene function. The enantioselectivity switch observed between (RS,SC)-11 and (RS,RC)-12 is explained by the inverted cis-trans coordinations of the substrate molecules in catalytic steps.
trans-Cyclooctenes as Chiral Ligands in Rhodium-Catalyzed Asymmetric 1,4-Additions
Nagano, Tagui,Einaru, Shunsuke,Shitamichi, Kenta,Asano, Keisuke,Matsubara, Seijiro
supporting information, p. 7131 - 7133 (2020/09/11)
trans-Cyclooctenes serve as asymmetric ligands for the rhodium-catalyzed 1,4-additions of organotin reagents to enones. We demonstrate, for the first time, that these chiral olefins can provide efficient coordination spheres for asymmetric metal catalysis. As the asymmetric environment around the reaction site is constructed by the trans-cyclooctene framework, the introduction of a substituent at the allylic position further improves enantioselectivity to 93 % ee. These findings provide new chiral framework designs for the asymmetric ligands of metal catalysts.
