- CHEMOSELECTIVE METHYLENE HYDROXYLATION IN AROMATIC MOLECULES
-
A chemoselective and reactive Mn(CF3-PDP) catalyst system that enables for the first time the strategic advantages of late-stage aliphatic C—H hydroxylation to be leveraged in aromatic compounds. This discovery will benefit small molecule therapeutics by enabling the rapid diversification of aromatic drugs and natural products and identification of their metabolites.
- -
-
Paragraph 0129; 0228
(2020/03/28)
-
- Mechanistic Insights into FLP-Catalyzed Iodoperfluoroalkylations
-
The frustrated Lewis pair-catalyzed iodoperfluoroalkylation of olefins, its substrate activation mode, and catalyst degradation pathways are mechanistically investigated by kinetic measurements. The transformation most likely proceeds via coordination of the phosphane to the perfluoroalkyl iodide and involves radical intermediates.
- Spittler, Michael,Helmecke, Lucas,Czekelius, Constantin
-
supporting information
p. 458 - 468
(2018/09/06)
-
- Fenton-Inspired C-H Functionalization: Peroxide-Directed C-H Thioetherification
-
Substoichiometric iron mediates the thioetherification of unactivated aliphatic C-H bonds directed by resident silylperoxides. Upon exposure to a catalytic amount of iron(II) triflate, TIPS-protected peroxides bearing primary, secondary, and tertiary C-H sites undergo chemoselective thioetherification of remote C-H bonds with diaryl disulfides. The reaction demonstrates a broad substrate scope and functional group tolerance without the use of any noble metal additives. Mechanistic experiments suggest that the reaction proceeds through 1,5-H atom abstraction by a hydroxyl radical generated with iron.
- Groendyke, Brian J.,Modak, Atanu,Cook, Silas P.
-
p. 13073 - 13091
(2019/10/10)
-
- N-Heterocyclic Carbene Iron(III) Porphyrin-Catalyzed Intramolecular C(sp3)–H Amination of Alkyl Azides
-
Metal-catalyzed intramolecular C?H amination of alkyl azides constitutes an appealing approach to alicyclic amines; challenges remain in broadening substrate scope, enhancing regioselectivity, and applying the method to natural product synthesis. Herein we report an iron(III) porphyrin bearing axial N-heterocyclic carbene ligands which catalyzes the intramolecular C(sp3)–H amination of a wide variety of alkyl azides under microwave-assisted and thermal conditions, resulting in selective amination of tertiary, benzylic, allylic, secondary, and primary C?H bonds with up to 95 % yield. 14 out of 17 substrates were cyclized selectively at C4 to give pyrrolidines. The regioselectivity at C4 or C5 could be tuned by modifying the reactivity of the C5–H bond. Mechanistic studies revealed a concerted or a fast re-bound mechanism for the amination reaction. The reaction has been applied to the syntheses of tropane, nicotine, cis-octahydroindole, and leelamine derivatives.
- Shing, Ka-Pan,Liu, Yungen,Cao, Bei,Chang, Xiao-Yong,You, Tingjie,Che, Chi-Ming
-
supporting information
p. 11947 - 11951
(2018/09/11)
-
- Electrophilic Zinc Homoenolates: Synthesis of Cyclopropylamines from Cyclopropanols and Amines
-
Metal homoenolates, produced via C-C bond cleavage of cyclopropanols, have been extensively investigated as nucleophiles for the synthesis of β-substituted carbonyl derivatives. Herein, we demonstrate that zinc homoenolates can react as carbonyl-electrophiles in the presence of nucleophilic amines to yield highly valuable trans-cyclopropylamines in good yields and high diastereoselectivities. GSK2879552, a lysine demethylase 1 inhibitor currently in clinical trials for the treatment of small cell lung carcinoma, was synthesized using this strategy.
- Mills, L. Reginald,Barrera Arbelaez, Luis Miguel,Rousseaux, Sophie A. L.
-
p. 11357 - 11360
(2017/08/30)
-
- PYRIDINE DERIVATIVES AS DGAT-1 INHIBITORS
-
Described herein are compounds of formula (I): The compounds of formula (I) act as DGAT1 inhibitors and can be useful in preventing, treating or acting as a remedial agent for hyperlipidemia, diabetes mellitus and obesity.
- -
-
Page/Page column 32
(2014/09/29)
-
- Thrombin inhibitors
-
Compounds of the invention are useful in inhibiting thrombin and associated thrombotic occlusions having the following structure: or a pharmaceutically acceptable salt thereof, wherein b is NY or O; c is CY2or N; d is CY3or N; e is CY4or N; f is CY5or N; g is CY6or N; Y4, Y5, and Y6are independently hydrogen, C1-4alkyl, or halogen; Y1and Y2are independently hydrogen, C1-4alkyl, C3-7cycloalkyl, halogen, NH2, OH or C1-4alkoxy, and Y3is hydrogen, C1-4alkyl, C3-7cycloalkyl, halogen, —CN, NH2, OH or C1-4alkoxy; A is and W, W1, R1, R3, R4, R5, X and Z are defined in the specification.
- -
-
-
- New cyclooxygenase-2/5-lipoxygenase inhibitors. 1. 7-tert-butyl-2,3- dihydro-3,3-dimethylbenzonfuran derivatives as gastrointestinal safe antiinflammatory and analgesic agents: Discovery and variation of the 5-keto substituent
-
A series of 5-keto-substituted 7-tert-butyl-2,3-dihydro-3,3- dimethylbenzofurans (DHDMBFs) were prepared and evaluated as potential nonsteroidal antiinflammatory and analgesic agents. Interest in this class of compounds arose when a DHDMBF was found to be
- Janusz, John M.,Young, Patricia A.,Ridgeway, James M.,Scherz, Michael W.,Enzweiler, Kevin,Wu, Laurence I.,Gan, Lixian,Darolia, Renuka,Matthews, Randall S.,Hennes, Duane,Kellstein, David E.,Green, Shelley A.,Tulich, Jennifer L.,Rosario-Jansen, Theresa,Magrisso, I. Jack,Wehmeyer, Kenneth R.,Kuhlenbeck, Deborah L.,Eichhold, Thomas H.,Dobson, Roy L. M.,Sirko, Steven P.,Farmer, Ralph W.
-
p. 1112 - 1123
(2007/10/03)
-
- Pyridine esters of cyclopropane-carboxylic acid
-
Heterocyclic organic esters and thioesters characterized by the presence of one or two cyclopropane moieties, synthesis thereof, and compositions thereof for the control of mites and ticks.
- -
-
-
- Control of Acarina by esters of cyclopropane acids
-
Methods and compositions for the control of Acarina employing esters of cyclopropane carboxylic acids described herein.
- -
-
-