- Directed Hydroxylation of sp2 and sp3 C-H Bonds Using Stoichiometric Amounts of Cu and H2O2
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The use of copper for C-H bond functionalization, compared to other metals, is relatively unexplored. Herein, we report a synthetic protocol for the regioselective hydroxylation of sp2 and sp3 C-H bonds using a directing group, stoichiometric amounts of Cu and H2O2. A wide array of aromatic ketones and aldehydes are oxidized in the carbonyl γ-position with remarkable yields. We also expanded this methodology to hydroxylate the β-position of alkylic ketones. Spectroscopic characterization, kinetics, and density functional theory calculations point toward the involvement of a mononuclear LCuII(OOH) species, which oxidizes the aromatic sp2 C-H bonds via a concerted heterolytic O-O bond cleavage with concomitant electrophilic attack on the arene system.
- Trammell, Rachel,D'Amore, Lorenzo,Cordova, Alexandra,Polunin, Pavel,Xie, Nan,Siegler, Maxime A.,Belanzoni, Paola,Swart, Marcel,Garcia-Bosch, Isaac
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p. 7584 - 7592
(2019/06/11)
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- Rhodium-Catalyzed Directing-Group-Assisted Aldehydic C–H Arylations with Aryl Halides
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A rhodium-catalyzed general protocol for the directing-group-assisted arylation of aromatic aldehydic C–H bonds was developed. This method involves either hydroxy- or amino-group-directed aldehyde C–H arylation with various aryl halides. A broad synthetic scope for the preparation of 2-hydroxybenzophenones was established with electronically variant salicylaldehydes and aryl halides with chemo- and regioselective possibilities. The developed protocol was also applied in the synthesis of medicinally important 3-salicyloylpyridines in high yields.
- Rao, Maddali L. N.,Ramakrishna, Boddu S.
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p. 5080 - 5093
(2017/09/20)
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- Palladium-catalyzed ortho-CH-bond oxygenation of aromatic ketones
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A palladium-catalyzed C(sp2)-H bond oxygenation reaction is described. This protocol represents the first example of a C-H bond cleavage/C-O bond formation sequence, by employing a ketone moiety as the directing group. With this new catalytic method, a variety of ortho-acylphenols can be easily accessed from arylketones.
- Choy, Pui Ying,Kwong, Fuk Yee
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supporting information
p. 270 - 273
(2013/03/13)
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- A new series of estrogen receptor modulators: Effect of alkyl substituents on receptor-binding affinity
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New types of selective estrogen receptor modulators (SERMs) were synthesized and evaluated for their binding affinity and biological effect on reproductive cells. A proposed lead structure (B) was derivatized to provide compounds 30 and 44, which showed g
- Kamada, Atsushi,Sasaki, Atsushi,Kitazawa, Noritaka,Okabe, Tadashi,Nara, Kazumasa,Hamaoka, Shinichi,Araki, Shin,Hagiwara, Hiroaki
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- SUNSCREEN COMPOSITIONS
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The present invention relates to improved sunscreen compositions, more preferably to improved sunscreen compositions containing at least one sunscreening agent (sunscreen) and a silicone-polyamide copolymer.
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- BeCl2 as a new highly selective reagent for dealkylation of aryl-methyl ethers
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An efficient and simple method is introduced for the selective removal of methyl group from poly aryl-methyl ethers, in some important derivatives of benzophenones, xanthones, anthraquinones, aryl esters, benzamides and nitroanisoles with BeCl2.
- Sharghi, Hashem,Tamaddon, Fatemeh
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p. 13623 - 13640
(2007/10/03)
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- Synthese von 4-Alkoxy-2-hydroxyphenylketoximen als Metallextraktions-Reagenzien
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The C-Acylation (Friedel-Crafts reaction) of resorcinol with aluminium chloride, the monoetherification in 4-position of the resulting 2,4-dihydroxyphenylketones, and the preparation of oximes (8, 9, 10, 11) from this ketones were investigated.The compounds obtained are characterized by elemental analysis, and the i.r., u.v. and 1H-n.m.r. spectra are discussed.Solubility data of some oximes are determined in water, octane and toluene.The extraction properties for copper-(II)-and iron-(III)-ions are measured by isotope methods in relation to the extragent structure, the extraction time and the pH-range.
- Beger, J.,Binte, H.-J.,Brunne, L.,Neumann, R.
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p. 269 - 277
(2007/10/02)
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