838-21-1Relevant academic research and scientific papers
Dirhodium-Catalyzed Enantioselective B?H Bond Insertion of gem-Diaryl Carbenes: Efficient Access to gem-Diarylmethine Boranes
Huang, Ming-Yao,Li, Xiao-Yu,Su, Yu-Xuan,Yang, Liang-Liang,Zhao, Yu-Tao,Zhu, Shou-Fei
supporting information, p. 24214 - 24219 (2021/10/07)
The scarcity of reliable methods for synthesizing chiral gem-diarylmethine borons limits their applications. Herein, we report a method for highly enantioselective dirhodium-catalyzed B?H bond insertion reactions with diaryl diazomethanes as carbene precursors. These reactions afforded chiral gem-diarylmethine borane compounds in high yield (up to 99 % yield), high activity (turnover numbers up to 14 300), high enantioselectivity (up to 99 % ee) and showed unprecedented broad functional group tolerance. The borane compounds synthesized by this method could be efficiently transformed into diaryl methanol, diaryl methyl amine, and triaryl methane derivatives with good stereospecificity. Mechanistic studies suggested that the borane adduct coordinated to the rhodium catalyst and thus interfered with decomposition of the diazomethane, and that insertion of a rhodium carbene (generated from the diaryl diazomethane) into the B?H bond was most likely the rate-determining step.
The cooperative effect of Lewis pairs in the Friedel-Crafts hydroxyalkylation reaction: A simple and effective route for the synthesis of (±)-carbinoxamine
Harikrishnan, Adhikesavan,Sanjeevi, Jayakumar,Ramanathan, Chinnasamy Ramaraj
, p. 3633 - 3647 (2015/03/30)
An efficient C-C bond formation strategy between aromatic/heteroaromatic π-nucleophiles and Lewis acid activated aldehydes is described. This aromatic electrophilic substitution reaction of arenes or heteroarenes is facilitated by Lewis acid AlBr3. Aromatic rings with electron donating substituents are excellent nucleophilic counterparts in this reaction, generating carbinols in excellent yields (61-94%). The formation of triarylmethanes is also witnessed in the case of certain reactive aldehydes and aromatic π-nucleophiles through reactive carbocation formation. The formation of triarylmethane is reduced to a greater extent via retardation of the second π-nucleophile addition through a Lewis base, for example, pyridine, coordination with an aluminium alkoxide intermediate. Various aliphatic aldehydes also underwent Friedel-Crafts type hydroxyalkylation and generated the expected carbinols in moderate yields (41-53%) in the presence of AlBr3. This protocol has been successfully applied to the synthesize of the (±)-carbinoxamine, a therapeutically important histamine H1 antagonist, in a one-pot manner.
A nontransmetalation reaction pathway for anionic four-electron donor-based palladacycle-catalyzed addition reactions of arylborons with aldehydes
Liao, Yuan-Xi,Xing, Chun-Hui,Israel, Matthew,Hu, Qiao-Sheng
supporting information; experimental part, p. 3324 - 3328 (2011/06/28)
A nontransmetalation reaction pathway for anionic four-electron donor-based (Type I) palladacycle-catalyzed addition reactions of arylborons with aldehydes is described. This new reaction pathway offers new catalysis opportunities for Type I palladacycle-catalyzed addition reactions such as the exceptionally low catalyst loading catalysis, with the catalyst loading as low as 0.0005 mol %. This new pathway may be applicable for other transition metal-catalyzed addition reactions and might lead to the development of new reactions including sequential/tandem reactions.
CATHEPSIN INHIBITORS
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Page/Page column 82, (2010/02/11)
This invention relates to a novel class of compounds, represented by the formula (I) below, wherein the meanings of R1, R2, R3 and R4 are indicated therein, which are cysteine protease inhibitors, including but not limited to, inhibitors of cathepsins K, L, S and B. These compounds are useful for treating diseases in which inhibition of bone resorption is indicated, such as osteoporosis, osteoarthritis and rheumatoid arthritis.
Synthesis and characterization of low generation halogenated linear poly(arylpropargyl)ether (PAPE) branches via selective palladium catalyzed coupling reactions
L'Hermite, Nathalie,Peyrat, Jean-Fran?ois,Alami, Mouad,Brion, Jean-Daniel
, p. 8987 - 8991 (2007/10/03)
A rapid convergent synthesis of first- and second-generation halogenated linear poly(arylpropargyl ether) branches 7 and 10 is described. The key step of the sequence studied involves a selective Sonogashira-Linstrumelle (S-L) cross-coupling reaction of a
Practical Method for the Rhodium-Catalyzed Addition of Aryl- and Alkenylboronic Acids to Aldehydes
Fuerstner, Alois,Krause, Helga
, p. 343 - 350 (2007/10/03)
The arylation or alkenylation of aldehydes will boronic acids is conveniently effected by a catalyst system comprising RhCl3 · 3 H2O (1 mol %), the sterically hindered imidazolium salt 2 (1 mol %), and a base. The N-heterocyclic carbene 6 derived from 2 is believed to be the actual ligand to the catalytically active rhodium species formed in situ. The method is compatible with various functional groups in both reaction partners and follows a non-chelation controlled pathway in additions to the Garner aldehyde 25.
Protonation of p-Methoxybenzhydryl Cations; a New Series of Indicators for Superacid Acidity Measurements by Nuclear Magnetic Resonance Spectroscopy
Touiti, Dominique,Jost, Roland,Sommer, Jean
, p. 1793 - 1798 (2007/10/02)
The behaviour of (p-substituted phenyl)(p-methoxyphenyl)methanol derivatives dissolved in superacid mixtures (HF, HFSO3, or CF3SO3H with various proportions of SbF5) has been studied by n.m.r. spectroscopy.Increasing the SbF5 concentration causes drastic changes in chemical shifts due to stable O-protonation of the methoxy group in the highest acidity media.By using these bases as indicators for superacid acidity measurements we have shown that the acidity of these three systems does not increase as fast as previously claimed, and also that the acidity of the CF3SO3H-SbF5 system remains lower than that of the HFSO3-SbF5 system in the 0-50percent SbF5 range.
