cas 85416-73-5, S- (+)-Rolipram | Articles data

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Multistep continuous-flow synthesis of (R)- and (S)-rolipram using heterogeneous catalysts
Chemical manufacturing is conducted using either batch systems or continuous-flow systems. Flow systems have several advantages over batch systems, particularly in terms of productivity, heat and mixing efficiency, safety, and reproducibility. However, fo
Tsubogo, Tetsu,Oyamada, Hidekazu,Kobayashi, Shu
p. 329 - 332
(2015)
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Enantioselective Flow Synthesis of Rolipram Enabled by a Telescoped Asymmetric Conjugate Addition-Oxidative Aldehyde Esterification Sequence Using in Situ-Generated Persulfuric Acid as Oxidant
A novel approach is reported for the enantioselective flow synthesis of rolipram comprising a telescoped asymmetric conjugate addition-oxidative aldehyde esterification sequence followed by trichlorosilane-mediated nitro group reduction and concomitant la
Nagy, Bence S.,Llanes, Patricia,Pericas, Miquel A.,Kappe, C. Oliver,?tv?s, Sándor B.
(2022/02/05)

Enantioselective Synthesis of Pyroglutamic Acid Esters from Glycinate via Carbonyl Catalysis
Direct α-functionalization of NH2-free glycinates with relatively weak electrophiles such as α,β-unsaturated esters still remains a big challenge in organic synthesis. With chiral pyridoxal 5 d as a carbonyl catalyst, direct asymmetric conjugated addition at the α-C of glycinate 1 a with α,β-unsaturated esters 2 has been successfully realized, to produce various chiral pyroglutamic acid esters 4 in 14–96 % yields with 81–97 % ee's after in situ lactamization. The trans and cis diastereomers can be obtained at the same time by chromatography and both of them can be easily converted into chiral 4-substituted pyrrolidin-2-ones such as Alzheimer's drug Rolipram (11) with the same absolute configuration via tert-butyl group removal and subsequent Barton decarboxylation.
Ma, Jiguo,Zhou, Qinghai,Song, Guanshui,Song, Yongchang,Zhao, Guoqing,Ding, Kuiling,Zhao, Baoguo
p. 10588 - 10592
(2021/04/06)

Synthesis method of flurolipram
The invention discloses a synthesis method of flurolipram, which comprises the following steps: carrying out catalytic reaction on a compound represented by formula 1 and an alcohol compound represented by formula II by using an N-heterocyclic carbene catalyst to generate an intermediate represented by formula 3.1 and/or 3.2, and carrying out a series of reactions on the intermediate represented by formula 3.1 and/or 3.2 to finally obtain flurolipram.The method is simple to operate, and the substrate is easy to prepare; reaction conditions are mild, and high yield and high stereoselectivity are achieved.
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Paragraph 0089-0102

(2021/03/13)

Efficient synthesis of (?)-(R)- and (+)-(S)-rolipram
A novel, efficient and protecting group free enantioselective synthetic approach of (?)-(R)-1 and (+)-(S)-rolipram 2 is described employing the organocatalyzed asymmetric Michael addition, Henry condensation, Wittig olefination and reductive lactamization
Kaur, Ramandeep,Pandey, Satyendra Kumar
p. 4333 - 4335
(2017/10/17)

Unprecedented hydrophobic amplification in noncovalent organocatalysis "on water": Hydrophobic chiral squaramide catalyzed michael addition of malonates to nitroalkenes
In this study, water was demonstrated to be an exceptionally efficient reaction medium for the noncovalent, hydrogen-bonding-promoted enantioselective Michael addition of malonates to diverse nitroolefins using cinchona-based squaramide catalysts. A significant increase in the reaction rate was observed when the reaction was performed "on water" rather than in the conventional organic solvents, because of the hydrophobic hydration effect. This hydrophobic amplification was significantly dependent upon the hydrophobicity of the C3-substituent (vinyl or ethyl) of cinchona-based catalysts. Thus, the use of more hydrophobic catalyst with an ethyl group at the C3-position, even a highly challenging Michael donor such as dimethyl methylmalonate was also smoothly converted to the desired adduct. Furthermore, because of the remarkable rate acceleration under "on water" conditions, the catalyst loading also significantly decreased. Thus, in the case of β-ketoesters, even 0.01 mol % of catalyst loading was enough to complete the reaction at room temperature, affording the corresponding Michael adducts with perfect diastereo- and enantioselectivity (up to >99:1 d.r., up to 99% ee). The developed "on water" protocol was successfully applied for the scalable syntheses of an antidepressant (S)-rolipram and an anticonvulsant (S)-pregabalin.
Bae, Han Yong,Song, Choong Eui
p. 3613 - 3619
(2015/06/16)

METHOD FOR PREPARING (R)-ROLIPRAM PRECURSOR BY CATALYTIC ENANTIOSELECTIVE MICAHEL REACTION AND METHOD FOR PREPARING (R)-ROLPTRAM USING THE (R)-ROLIPRAM PRECURSOR
According to the present invention, a method for preparing chiral (R)-rolipram precursors includes a step of enabling an asymmetric Michael reaction of 3-(cyclo pentoxy)-4-methoxyphenyl nitro and malonate in the presence of a soluble chiral catalyst. Accordingly, the present invention can synthesize chiral (R)-rolipram precursors at low costs by using an organic catalyst not including transition metals with high optical selectivity and reactivity in the presence of water, aqueous solution, or a mixed solution of an organic solvent which are not harmful to the human body and do not cause environmental pollution.COPYRIGHT KIPO 2015
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Paragraph 0072-0074

(2016/10/27)

METHOD OF PREPARING PHARMACEUTICAL BY CONTINUOUS FLOW MULTI-STAGE REACTION
PROBLEM TO BE SOLVED: To obtain optic active compounds efficiently by incorporating, into a multi-stage flow synthesis system, a column provided with a solid-phase synthesis device necessary for synthesizing optic active compounds to become pharmaceutical
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Paragraph 0033

(2016/10/07)

Multisite organic-inorganic hybrid catalysts for the direct sustainable synthesis of GABAergic drugs
Multisite organic-inorganic hybrid catalysts have been prepared and applied in a new general, practical, and sustainable synthetic procedure toward industrially relevant GABA derivatives. The domino sequence is composed of seven chemical transformations which are performed in two one-pot reactions. The method produces both enantiomeric forms of the product in high enantiopurity as well as the racemate in good yields after a single column purification step. This protocol highlights major process intensification, catalyst recyclability, and low waste generation.
Leyva-Perez, Antonio,Garcia-Garcia, Pilar,Corma, Avelino
supporting information
p. 8687 - 8690
(2014/08/18)

A simple enantioselective route toward (R)- and (S)-Rolipram via anhydride desymmetrization
A highly enantioselective metal-free synthesis of both enantiomers of Rolipram is reported. The key stereoinductive step is a cinchona alkaloid catalyzed opening of a cyclic anhydride prepared from isovanillin, where both enantiomers are available using t
Ivsic, Trpimir,Hamersak, Zdenko
p. 217 - 222
(2013/04/23)

Elucidation of a structural basis for the inhibitor-driven, p62 (SQSTM1)-dependent intracellular redistribution of cAMP phosphodiesterase-4A4 (PDE4A4)
Figure Presented. A survey of PDE4 inhibitors reveals that some compounds trigger intracellular aggregation of PDE4A4 into accretion foci through association with the ubiquitin-binding scaffold protein p62 (SQSTM1). We show that this effect is driven by i
Day, Jonathan P.,Lindsay, Barbara,Riddell, Tracy,Jiang, Zhong,Allcock, Robert W.,Abraham, Achamma,Sookup, Sebastian,Christian, Frank,Bogum, Jana,Martin, Elisabeth K.,Rae, Robert L.,Anthony, Diana,Rosair, Georgina M.,Houslay, Daniel M.,Huston, Elaine,Baillie, George S.,Klussmann, Enno,Houslay, Miles D.,Adams, David R.
p. 3331 - 3347
(2011/07/09)

Rhodium-catalyzed asymmetric addition of arylboronic acids to γ-phthalimido-substituted-α,β-unsaturated carboxylic acid esters: An approach to γ-amino acids
Efficient Rh-catalyzed asymmetric 1,4-addition of arylboronic acids to ethyl-γ-phthalimidocrotonate by using bis-sulfoxide ligand affords γ-aminobutyric acid (GABA) derivatives with high enantioselectivities (90-96% ee) under mild conditions. Optically pu
Han, Fuzhong,Chen, Jun,Zhang, Xiangyang,Liu, Jibing,Cun, Linfeng,Zhu, Jin,Deng, Jingen,Liao, Jian
supporting information; experimental part
p. 830 - 833
(2011/03/20)

A heterobimetallic Ni/La-salan complex for catalytic asymmetric decarboxylative 1,4-addition of malonic acid half-thioester
Not salen, but salan: A new dinucleating salan-type ligand 1 was developed for the enantioselective decarboxylative 1,4-addition of malonic acid half-thioester to nitroalkenes. A Ni/La/1 complex gave products in 99-40% yield and 94-66% ee.
Furutachi, Makoto,Mouri, Shinsuke,Matsunaga, Shigeki,Shibasaki, Masakatsu
supporting information; experimental part
p. 2351 - 2354
(2011/06/25)

Water-compatible iminium activation: Organocatalytic Michael reactions of carbon-centered nucleophiles with enals
(Chemical Equation Presented) A pool of water-compatible catalysts, namely the chiral prolinol-based catalysts 1, has been developed for highly enantioselective C-C bond-forming Michael reactions in water (see scheme). The synthesis of (S)-Rolipram, a type IV phosphodiesterase inhibitor, was also demonstrated.
Palomo, Claudio,Landa, Aitor,Mielgo, Antonia,Oiarbide, Mikel,Puente, Angel,Vera, Silvia
p. 8431 - 8435
(2008/09/19)

Co-catalyzed reductive cyclization of azido and cyano substituted α,β-unsaturated esters with NaBH4: enantioselective synthesis of (R)-baclofen and (R)-rolipram
Sodium borohydride in combination with a catalytic amount of CoCl2 has been found to be an excellent catalytic system in reductive cyclizations of suitably substituted azido and cyano groups of α,β-unsaturated esters to afford γ and δ-lactams in high yields. The process has been demonstrated for the enantioselective synthesis of (R)-baclofen, (R)-rolipram, and (R)-4-fluorophenylpiperidinone, a key intermediate for (-)-paroxetine.
Paraskar, Abhimanyu S.,Sudalai, Arumugam
p. 4907 - 4916
(2007/10/03)

Synthesis of 4-aryl-2-pyrrolidones and β-aryl-γ-amino-butyric acid (GABA) analogues by Heck arylation of 3-pyrrolines with arenediazonium tetrafluoroborates. Synthesis of (±)-rolipram on a multigram scale and chromatographic resolution by semipreparative chiral simulated moving bed chromatography
(Chemical Equation Presented) We report herein a new, practical, and economic synthesis of the phosphodiesterase inhibitor Rolipram on a multigram scale as well as the synthesis of new 4-aryl pyrrolidones and β-aryl-γ-amino butyric acids (GABA derivatives) employing an efficient Heck-Matsuda arylation of 3-pyrroline with aryldiazonium tetrafluoroborates. Racemic Rolipram was resolved into its enantiomers using chiral simulated moving bed chromatography having the low-cost microcrystalline cellulose triacetate as a chiral stationary phase.
Garcia, Ariel L. L.,Carpes, Marcos J. S.,De Oca, Antonio C. B. M.,Dos Santos, Marco A. G.,Santana, Cesar C.,Correia, Carlos Roque D.
p. 1050 - 1053
(2007/10/03)

Dirhodium catalyzed intramolecular enantioselective C-H insertion reaction of N-cumyl-N-(2-p-anisylethyl)diazoacetamide: Synthesis of (-)-Rolipram
Cumyl(2,2-dimethyl-benzyl) was used as an N-protecting group for intramolecular C-H insertion reaction of α-diazoacetamide. Excellent chemoselectivity (>98:2) in C-H insertion over the aromatic addition of N-cumyl-N-(2-p-anisylethyl)diazoacetamide was obtained with Rh 2[(4S)-MEOX)]4 catalyst in moderate enantioselectivity (53% ee). The reaction was successfully applied in the synthesis of (-)-Rolipram in 15% total yield.
Liu, Wei-Jun,Chen, Zhen-Liang,Chen, Zhi-Yong,Hu, Wen-Hao
p. 1693 - 1698
(2007/10/03)

Enantioselective Syntheses of (-)-(R)-Rolipram, (-)-(R)-Baclofen and Other GABA Analogues via Rhodium-Catalyzed Conjugate Addition of Arylboronic Acids
Highly enantioselective syntheses of two important γ-aminobutyric acid (GABA) analogues, the antispastic drug (-)-(R)-Baclofen and the antidepressant agent (-)-(R)-Rolipram, are reported. Key-steps in both syntheses are the Rh-catalyzed asymmetric 1,4-additions of arylboronic acids to 4-aminobut-2,3-enoic acid derivatives.
Becht, Jean-Michel,Meyer, Oliver,Helmchen, Guenter
p. 2805 - 2810
(2007/10/03)

Development of a catalytic enantioselective conjugate addition of 1,3-dicarbonyl compounds to nitroalkenes for the synthesis of endothelin-A antagonist ABT-546. Scope, mechanism, and further application to the synthesis of the antidepressant rolipram
The enantioselective synthesis of endothelin-A antagonist ABT-546 has been accomplished via the discovery and development of a highly selective catalytic asymmetric conjugate addition of ketoesters to nitroolefins. Employing just 4 mol % bis(oxazoline)-Mg
Barnes, David M.,Wittenberger, Steven J.,Zhang, Ji,Ji, Jianguo,Fickes, Michael G.,Fitzgerald, Michael A.,King, Steven A.,Morton, Howard E.,Plagge, Frederick A.,Preskill, Margo,Wagaw, Seble H.
p. 13097 - 13105
(2007/10/03)

First highly regio- and diastereoselective [3+2] cycloaddition of chiral nonracemic Fischer carbene complexes with azomethine ylides: An enantioselective synthesis of (+)-Rolipram
A new procedure for the synthesis of 1,3,4-trisubstituted and 1,4-di-substituted pyrrolidin-2-one derivatives in an enantioselective fashion is reported. The 1,3-dipolar cycloaddition of (±)-menthol and (-)-8-phenylmenthol derived Fischer alkoxy alkenyl carbene complexes with in situ generated functionalized azomethine ylides gives the corresponding cycloadducts as chelated tetracarbonyl Fischer carbene complexes. Only one regioisomer is detected in all cases, and the diastereoselectivity of the reaction is very high when (-)-8-phenylmenthol derived carbenes are employed. Oxidation and further transformation of the cycloadducts provide an easy access to pyrrolidin-2-ones. The anti-inflammatory and antidepressant drug (+)-Rolipram is readily prepared in four steps in a 20% overall yield by taking advantage of this newly developed methodology.
Barluenga, Jose,Fernandez-Rodriguez, Manuel A.,Aguilar, Enrique,Fernandez-Mari, Felix,Salinas, Alejandro,Olano, Bernardo
p. 3533 - 3544
(2007/10/03)

The Crystal Structure, Absolute Configuration, and Phosphodiesterase Inhibitory Activity of (+)-1-(4-Bromobenzyl)-4-(3-(cyclopentyloxy)-4-methoxyphenyl)-pyrrolidin-2-one
Chiral HPLC resolution of the phosphodiesterase IV (PDE IV) inhibitor rolipram (1) provided (-)-1, and this enantiomer was converted into its 1-(4-bromobenzyl) derivative, (+)-2.X-ray structural analysis of (+)-2 establishad the absolute configuration as
Baures, Paul W.,Eggleston, Drake S.,Erhard, Karl F.,Cieslinski, Lenora B.,Torphy, Theodore J.,Christensen, Siegfried B.
p. 3274 - 3277
(2007/10/02)