- Development of Novel Phosphino-Oxazoline Ligands and Their Application in Asymmetric Alkynlylation of Benzylic Halides
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A new set of stereochemically diverse phosphino-oxazoline ligands derived from simple L-amino acids and 2-(diphenylphosphaneyl)benzoic acid were developed. Those mono anionic tridentated N,N,P-ligands promote the Cu-catalyzed enantioselective radical coupling of terminal alkynes with a broad range of benzylic halides including benzo-fused cyclic α-halides and α-silyl benzyl halides in high yield and excellent enantioselectivity under mild reaction conditions. With multi distinct sites for structural modification, a diverse pool of chiral N,N,P-ligands is readily accessed, allowing for rapid optimization of the ligand structure for a specific substrate. Notably, the enantioselective alkynlylation of benzylic halides bonds in benzo-cyclic molecules has also been realized for the first time.
- Guo, Rui,Li, Junxia,Sang, Jiale,Xiao, Haijing,Zhang, Guozhu
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supporting information
(2022/03/27)
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- Chemoselective Oxidation of Equatorial Alcohols with N-Ligated λ3-Iodanes
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The site-selective and chemoselective functionalization of alcohols in complex polyols remains a formidable synthetic challenge. Whereas significant advancements have been made in selective derivatization at the oxygen center, chemoselective oxidation to the corresponding carbonyls is less developed. In cyclic systems, whereas the selective oxidation of axial alcohols is well known, a complementary equatorial selective process has not yet been reported. Herein we report the utility of nitrogen-ligated (bis)cationic λ3-iodanes (N-HVIs) for alcohol oxidation and their unprecedented levels of selectivity for the oxidation of equatorial over axial alcohols. The conditions are mild, and the simple pyridine-ligated reagent (Py-HVI) is readily synthesized from commercial PhI(OAc)2 and can be either isolated or generated in situ. Conformational selectivity is demonstrated in both flexible 1,2-substituted cyclohexanols and rigid polyol scaffolds, providing chemists with a novel tool for chemoselective oxidation.
- Mikhael, Myriam,Adler, Sophia A.,Wengryniuk, Sarah E.
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supporting information
p. 5889 - 5893
(2019/08/26)
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- 3-(2,3-DIHYDRO-1H-INDEN-5-YL)PROPANOIC ACID DERIVATIVES AND THEIR USE AS NRF2 REGULATORS
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The present invention relates to compounds of Formula (I), and Formula (II), wherein B is benzotriazolyl, phenyl, triazolopyridinyl, or -(CH2)2-triazolyl each of which may be unsubstituted or substituted by 1, 2, or 3 substituents independently chosen from -C1-3 alkyl, -O-C1-3 alkyl, CN, - (CH2)2-O-(CH2)2-OR4 and halo; and D is -C(O)OH, -C(O)NHSO2CH3, -SO2NHC(O)CH3, 5-(trifluoromethyl)-4H-1,2,4-triazol-2-yl, or tetrazolyl; and their use as NRF2 regulators.
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Page/Page column 212
(2018/06/30)
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- (Poly)cationic λ3-Iodane-Mediated Oxidative Ring Expansion of Secondary Alcohols
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Herein, a simplified approach to the synthesis of medium-ring ethers through the electrophilic activation of secondary alcohols with (poly)cationic λ3-iodanes (N-HVIs) is reported. Excellent levels of selectivity are achieved for C–O bond migration over established α-elimination pathways, enabled by the unique reactivity of a novel 2-OMe-pyridine-ligated N-HVI. The resulting hexafluoroisopropanol (HFIP) acetals are readily derivatized with a range of nucleophiles, providing a versatile functional handle for subsequent manipulations. The utility of this methodology for late-stage natural product derivatization was also demonstrated, providing a new tool for diversity-oriented synthesis and complexity-to-diversity (CTD) efforts. Preliminary mechanistic investigations reveal a strong effect of alcohol conformation on the reactive pathway, thus providing a predictive power in the application of this approach to complex molecule synthesis.
- Walters, Jennifer C.,Tierno, Anthony F.,Dubin, Aimee H.,Wengryniuk, Sarah E.
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supporting information
p. 1460 - 1464
(2018/04/06)
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- NRF2 REGULATORS
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The present invention relates to aryl analogs, pharmaceutical compositions containing them and their use as Nrf2 regulators.
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Page/Page column 211
(2017/01/02)
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- Condensed derivatives of imidazole useful as pharmaceuticals
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The invention relates to the compounds (I) and their acids and bases salts: wherein: the dotted line indicates a double bond; X is N or C-R1 and Y is N or C-R2, X and Y not being simultaneously N; A is selected from the group consisting of phenyl, naphthyl and (5-11) membered monocyclic or bicyclic unsaturated cycle or heterocycle possibly substituted as defined in the application, and A can also comprise either a further (4-7) membered heterocycle, said heterocycle being a monocycle, fused, saturated or unsaturated, the polycyclic system then comprising up to 14 members and up to 5 heteroatoms selected from N, O and S; B is Hydrogen or a substituent as defined in the application, or B is a (4-10) membered mono or bicyclic saturated or unsaturated heterocycle containing 1-3 heteroatoms selected from N, O and S, and possibly substituted as defined in the application; B not being Hydrogen when X is N and Y is C-R2; R1 is Hydrogen or a substituent as defined in the application; B and R1 cannot be simultaneously Hydrogen; R2 is Hydrogen or Halogen; their preparation, their use in the antibacterial prevention and therapy, alone or in association with antibacterials, antivirulence agents or drugs reinforcing the host innate immunity, and pharmaceutical compositions and associations containing them.
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Paragraph 0569
(2015/09/23)
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- Catalytic asymmetric intermolecular bromoesterification of unfunctionalized olefins
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An asymmetric intermolecular bromoesterification of unfunctionalized olefins catalyzed by (DHQD)2PHAL is described. Optically active bromoesters can be obtained with up to 92% ee.
- Li, Lijun,Su, Cunxiang,Liu, Xiaoqin,Tian, Hua,Shi, Yian
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supporting information
p. 3728 - 3731
(2014/08/05)
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- Direct oxidative allylic and vinylic amination of alkenes through selenium catalysis
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Bringing "N" into the game: The direct chemoselective nitrogenation of unactivated alkenes can be achieved through oxidative selenium catalysis (see scheme). This method provides a broad variety of allylic imides in yields of up to 89 % using N-fluorobenzenesulfonimide (NFSI) as the terminal oxidant and nitrogen source. Furthermore, an unprecedented selenium-catalyzed vinylic C(sp2)-H nitrogenation was discovered. Copyright
- Trenner, Johanna,Depken, Christian,Weber, Thomas,Breder, Alexander
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supporting information
p. 8952 - 8956
(2013/09/02)
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- Cathepsin S Inhibitor Compounds
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The present invention provides a compound of Formula (I): or a pharmaceutically acceptable salt thereof. Also, the present invention provides a pharmaceutical composition comprising a compound of Formula (I) or a pharmaceutically acceptable salt thereof with a pharmaceutically acceptable diluent or carrier. The present invention further provides methods for treating abdominal aortic aneurysm, plaque instability, atherosclerosis, or autoimmune disorders such as rheumatoid arthritis, psoriasis, and lupus comprising administering a therapeutically effective amount of a compound of Formula (I) or a pharmaceutically acceptable salt thereof or a pharmaceutical composition comprising a compound of Formula (I) or pharmaceutically acceptable salt thereof and a pharmaceutically acceptable diluent or carrier.
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Page/Page column 7
(2012/04/23)
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- FUNCTIONALLY SELECTIVE ALPHA2C ADRENORECEPTOR AGONISTS
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In its many embodiments, the present invention provides a novel class of biaryl compounds as inhibitors of ?2C adrenergic receptor agonists, methods of preparing such compounds, pharmaceutical compositions containing one or more such compounds, methods of
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Page/Page column 37
(2010/08/08)
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- ORGANIC COMPOUNDS
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The present invention provides a compound of formula I: said compound is inhibitor of aldosterone synthase (CYP11B2), and/or 11beta-hydroxylase (CYP11B1), and/or aromatase, and thus can be employed for the treatment of a disorder or disease mediated by al
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Page/Page column 72-73
(2008/12/06)
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- Piperazine compounds
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A compound selected from those of formula (I): wherein: R1, R2, R3 and R4, which may be the same or different, each represent an atom or group selected from hydrogen, halogen, alkyl, alkoxy, phenyl and cyano, X represents a bond, an oxygen atom or a group selected from —(CH2)m—, —OCH2— and —NR5—, wherein m represents 1 or 2, and R5 is as defined in the description, Y represents an oxygen atom or a group selected from NR7 and CHR8, wherein R7 and R8 are as defined in the description, Z represents a nitrogen atom or a CH group, n represents 1 or 2, Ak represents an alkylene chain, Ar represents an aryl or heteroaryl group, its optical isomers, and addition salts thereof with a pharmaceutically acceptable acid. Medical products containing the same which are useful in the treatment of conditions requiring a serotonin reuptake inhibitor and/or NK1 antagonist.
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Page/Page column 6-7
(2008/06/13)
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- AROMATIC SUBSTITUENT EFFECT ON THE STEREOSELECTIVITY OF THE ACID-INDUCED RING OPENING OF 1,2-EPOXIDES DERIVED FROM 3,4-DIHYDRONAPHTHALENE. IMPORTANCE OF THE REACTIVE CONFORMATIONS FOR THE STEREOSELECTIVITY.
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The stereochemistry of the acid-induced ring opening reactions (hydrolysis, methanolysis and trichloroacetolysis) of 1,2-epoxides derived from ring substituted 3,4-dihydronaphthalene has been examined.In every case, a satisfactory Hammett-type linear correlation was found between the diastereoselectivity of the reaction and the ?+ constant of the aromatic substituent.The stereoselectivity of the opening reaction turned out to be largely driven by the reactive conformation of the epoxide and/or of the opening process intermediates.
- Chini, Marco,Crotti, Paolo,Minutolo, Filippo,Martinelli, Adriano,Micali, Eugenio
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- Synthesis of Biological Markers in Fossil Fuels. 2. Synthesis and 13C NMR Studies of Substituted Indans and Tetralins
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Unambiguous syntheses of all possible methyl, ethyl, n-propyl, and n-butyl derivatives of indan and tetralin were developed using the Kumada coupling procedure involving the reaction of aryl or vinyl halides with Grignard reagents in the presence of nickel(II) chloride.An analysis of the 13C NMR spectra of these compounds was also completed.
- Adamczyk, Maciej,Watt, David S.,Netzel, Daniel A.
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p. 4226 - 4237
(2007/10/02)
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- Synthesis and Immunological Activity of 5,6,6a,8,9,11a-Hexahydronaphthimidazothiazoles and 5,6,6a,9,10,11a-Hexahydronaphthimidazothiazoles
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A series of 5,6,6a,8,9,11a-hexahydronaphthimidazothiazoles (17 and 20) and 5,6,6a,9,10,11a-hexahydronaphthimidazothiazoles (18) has been synthesized with cis- and/or trans-1,2-diamino-1,2,3,4-tetrahydronaphthalenes (12) as the key intermediates and subsequently evaluated for immunological activity (effects on antibody formation and delayed-type hypersensitivity reaction).Among the compounds tested, trans-5,6,6a,8,9,11a-hexahydronaphthimidazo(2,1-b>thiazole (trans-17a) and (+/-)-5,6,6aβ-8,9,11aα-hexahydro-8β-hydroxy-9β-methyl-8α-phenylnaphthimidazothiazole (20a) showed the largest immunological activity in mice with a magnitude comparable to that of levamisole and were found to be considerably less toxic than levamisole in an acute toxicological study.The structures of 18a and 20a were determined by X-ray crystallography.
- Saito, Masahiko,Kayama, Yasutaka,Watanabe, Tamaki,Fukushima, Hisashi,Hara, Takeshi,et al.
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p. 1364 - 1372
(2007/10/02)
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