76671-56-2Relevant academic research and scientific papers
Planar chiral [2.2]paracyclophane-based bisoxazoline ligands: Design, synthesis, and use in cu-catalyzed inter- and intramolecular asymmetric O-H insertion reactions
Kitagaki, Shinji,Murata, Shunsuke,Asaoka, Kisaki,Sugisaka, Kenta,Mukai, Chisato,Takenaga, Naoko,Yoshida, Keisuke
, p. 1006 - 1014 (2018/10/08)
Centrally chiral bisoxazolines connected directly to a planar chiral [2.2]paracyclophane backbone were synthesized and evaluated as asymmetric ligands in Cu-catalyzed intermolecular ethanolic O-H insertion reactions of α-diazo esters. The reactivities and enantioselectivities of Cu complexes of the synthesized bisoxazoline ligands were lower than those of ligands without central chirality. However, planar chiral [2.2] paracyclophane-based bisoxazoline ligands with an inserted benzene spacer that had a sterically demanding isopropyl substituent showed good enantioselectivities in inter- and intramolecular aromatic O-H insertion reactions, without the aid of central chirality.
Design and Synthesis of N-Aryl Phenoxyethoxy Pyridinones as Highly Selective and CNS Penetrant mGlu3 NAMs
Engers, Julie L.,Bollinger, Katrina A.,Weiner, Rebecca L.,Rodriguez, Alice L.,Long, Madeline F.,Breiner, Megan M.,Chang, Sichen,Bollinger, Sean R.,Bubser, Michael,Jones, Carrie K.,Morrison, Ryan D.,Bridges, Thomas M.,Blobaum, Anna L.,Niswender, Colleen M.,Conn, P. Jeffrey,Emmitte, Kyle A.,Lindsley, Craig W.
supporting information, p. 925 - 930 (2017/09/23)
Herein, we detail the optimization of the mGlu3 NAM, VU0650786, via a reductionist approach to afford a novel, simplified mGlu3 NAM scaffold that engenders potent and selective mGlu3 inhibition (mGlu3 IC50
Acylative kinetic resolution of racemic heterocyclic amines with (R)-2-phenoxypropionyl chloride
Vakarov, Sergey A.,Gruzdev, Dmitry A.,Chulakov, Evgeny N.,Sadretdinova, Liliya Sh.,Tumashov, Andrey A.,Pervova, Marina G.,Ezhikova, Marina A.,Kodess, Mikhail I.,Levit, Galina L.,Krasnov, Victor P.,Charushin, Valery N.
supporting information, p. 1231 - 1237 (2016/11/23)
The acylative kinetic resolution of racemic heterocyclic amines such as 3,4-dihydro-3-methyl-2H-[1,4]benzoxazines, 3,4-dihydro-3-methyl-2H-[1,4]benzothiazine, 2-methyl-1,2,3,4-tetrahydro-quinolines and 2-methylindoline with enantiopure (R)-2-phenoxypropionyl chloride has been studied. It has been found that acylation of 3,4-dihydro-3-methyl-2H-[1,4]benzothiazine proceeds with the best stereoselectively when compared with other racemic amines. An efficient method for the preparation of (S)-3,4-dihydro-3-methyl-2H-[1,4]benzothiazine (99.4% ee) via a kinetic resolution protocol was developed. The possibility of recycling (R)-2-phenoxypropionic acid has been demonstrated.
Advances and mechanistic insight on the catalytic Mitsunobu reaction using recyclable azo reagents
Hirose, Daisuke,Gazvoda, Martin,Ko?mrlj, Janez,Taniguchi, Tsuyoshi
, p. 5148 - 5159 (2016/07/29)
Ethyl 2-arylhydrazinecarboxylates can work as organocatalysts for Mitsunobu reactions because they provide ethyl 2-arylazocarboxylates through aerobic oxidation with a catalytic amount of iron phthalocyanine. First, ethyl 2-(3,4-dichlorophenyl)hydrazinecarboxylate has been identified as a potent catalyst, and the reactivity of the catalytic Mitsunobu reaction was improved through strict optimization of the reaction conditions. Investigation of the catalytic properties of ethyl 2-arylhydrazinecarboxylates and the corresponding azo forms led us to the discovery of a new catalyst, ethyl 2-(4-cyanophenyl)hydrazinecarboxylates, which expanded the scope of substrates. The mechanistic study of the Mitsunobu reaction with these new reagents strongly suggested the formation of betaine intermediates as in typical Mitsunobu reactions. The use of atmospheric oxygen as a sacrificial oxidative agent along with the iron catalyst is convenient and safe from the viewpoint of green chemistry. In addition, thermal analysis of the developed Mitsunobu reagents supports sufficient thermal stability compared with typical azo reagents such as diethyl azodicarboxylate (DEAD). The catalytic system realizes a substantial improvement of the Mitsunobu reaction and will be applicable to practical synthesis.
Asymmetric O–H insertion reaction of carbenoids catalyzed by chiral bicyclo bisoxazoline copper(I) and (II) complexes
Le Maux, Paul,Carrié, Daniel,Jéhan, Philippe,Simonneaux, Gérard
, p. 4671 - 4675 (2016/07/18)
Chiral copper(I) and (II)-bicyclobisoxazoline complexes were found to catalyze the insertion of α-diazocarbonyl compounds into O–H bonds of alcohols. The insertion reactions of various α-diazopropionates proceeded with moderate yields (40–90%) and high enantioselectivities (up to 92% and 94% with copper(I) and copper(II)-catalysts, respectively). A predominant effect on the enantiocontrol of the reaction was observed when copper(I) and (II)-catalysts were associated with NaBARF and molecular sieves (4??).
Synthesis of planar chiral [2.2]paracyclophane-based bisoxazoline ligands bearing no central chirality and application to Cu-catalyzed asymmetric O-H insertion reaction
Kitagaki, Shinji,Sugisaka, Kenta,Mukai, Chisato
, p. 4833 - 4836 (2015/05/05)
C2-symmetric planar chiral [2.2]paracyclophane-based bisoxazoline ligands, characterized by the inserted benzene spacer, which has a sterically demanding substituent, were synthesized and it was shown that up to 80% ee was obtained for the Cu-catalyzed O-H insertion reaction of α-diazo esters without the aid of the central chirality.
Resolution of (R, S)-ethyl-2-(4-hydroxyphenoxy) propanoate using lyophilized mycelium of Aspergillus oryzae WZ007
Zheng, Jian-Yong,Wu, Jia-Yu,Zhang, Yin-Jun,Wang, Zhao
, p. 62 - 66 (2013/10/01)
The mycelium of Aspergillus oryzae WZ007 was successfully developed to kinetic resolution of (R, S)-ethyl-2-(4-hydroxyphenoxy) propanoate ((R, S)-EHPP) for production of (R)-ethyl-2-(4-hydroxyphenoxy) propanoate ((R)-EHPP). The key biocatalytic process parameters (pH, temperature, rotation speed and substrate concentration) were optimized. Under the optimum conditions, the optical purity of (R)-EHPP was improved up to >99% when the conversion was above 49%. A. oryzae WZ007 whole-cell lipase exhibited high reaction capacity, enantioselectivity and good reusability. The tolerable substrate concentration was 0.5 mol/L, and dry mycelium of A. oryzae WZ007 maintains over 80% of its initial activity after eight repeating cycles. Therefore the enzymatic preparation of (R)-EHPP route was suitable for industrial application.
Preparation of novel chiral non-racemic diselenides and applications in asymmetric synthesis
Zhao, Liwei,Li, Zhong,Wirth, Thomas
experimental part, p. 176 - 182 (2011/03/22)
New chiral non-racemic diselenides were prepared and their corresponding selenium electrophiles were used for thestereoselective functionalization of alkenes. The influence of different nucleophiles on the outcome of the selenenylation reaction was studie
Rapid and efficient synthesis of (R)-aryloxypropionic acid esters under microwave irradiation
Ochal, Zbigniew,Durka, Krzysztof,Banach, Lukasz
experimental part, p. 3209 - 3213 (2010/12/24)
A series of (R)-(+)-ethyl aryloxypropionates (4a-4p) have been synthesized by the reaction of substituted phenols with ethyl (S)-(-)-tosyloxy lactate under the conditions of microwave irradiation and without solvents. The reaction conditions have been optimized. A good method for the preparation of (R)-(+)-ethyl aryloxypropionate was developed, with good yields, high enantiomer excess, short reaction times, easy workup, and simple procedure. Copyright Taylor & Francis Group, LLC.
Stereospecific synthesis and bio-activity of novel β3-adrenoceptor agonists and inverse agonists
Perrone, Maria Grazia,Santandrea, Ernesto,Bleve, Laura,Vitale, Paola,Colabufo, Nicola Antonio,Jockers, Ralf,Milazzo, Ferdinando Maria,Sciarroni, Anna Floriana,Scilimati, Antonio
, p. 2473 - 2488 (2008/09/21)
Since it is widely distributed into the body, β3-adrenoceptor is becoming an attractive target for the treatment of several pathologies such as obesity, type 2 diabetes, metabolic syndrome, cachexia, overactive bladder, ulcero-inflammatory disorder of the gut, preterm labour, anxiety and depressive disorders, and heart failure. New compounds belonging to the class of arylethanolamines bearing one or two stereogenic centres were prepared in good yields as racemates and optically active forms. They were, then, evaluated for their intrinsic activity towards β3-adrenoceptor and their affinity for β1- and β2-adrenergic receptors. Stereochemical features were found to play a crucial role in determining the behaviour of such compounds. In particular, α-racemic, (αR)- and (αS)-2-{4-[2-(2-hydroxy-2-phenylethylamino)ethyl]phenoxy}-2- methylpropanoic acid, (α-rac, β-rac)-, (αR, βS)- and (αR, βR)- 2-{4-[2-(2-hydroxy-2-phenylethylamino)ethyl]phenoxy}propanoic acid were found to be endowed with β3-adrenoceptor agonistic activity. Whereas, (αS, βS)- and (αS, βR)-2-{4-[2-(2-hydroxy-2-phenylethylamino)ethyl]phenoxy}propanoic acid behaved as β3-adrenoceptor inverse agonists. Such compounds showed no affinity for β1- and β2-adrenergic receptor, respectively. Thus, resulting highly selective β3-adrenoceptor ligands.
