A new and efficient chemoenzymatic access to both enantiomers of 4-hydroxycyclopent-2-en-1-one

Demir, Ayhan S.,Sesenoglu, Ozge

, p. 667 - 670 (2002)

A chemoenzymatic synthesis of both enantiomers of pharmacologically interesting 4-hydroxycyclopent-2-en-1-one in three steps starting from 3-methoxycyclopent-2-en-1-one is described. Manganese(III) acetate-mediated acetoxylation followed by enzyme-mediate

Synthesis of 6-Substituted 2-Pyrones Starting from Renewable Resources: Total Synthesis of Sibirinone, (E)-6-(Pent-1-en-1-yl)-2H-pyran-2-one, and (E)-6-(Hept-1-en-1-yl)-2H-pyran-2-one

Dobler, Daniel,Reiser, Oliver

, p. 10357 - 10365 (2016)

An atom-economic reaction sequence to 6-substituted 2-pyrones was developed starting from furfuryl alcohol, a renewable resource made from bran or bagasse, and aldehydes, utilizing a thermal rearrangement of cyclopentadienone epoxides as key step. Derivatives bearing a hydroxyalkyl side chain could be enzymatically resolved, providing access to enantiomerically pure 2-pyrones, or converted to alkenyl-substituted 2-pyrones such as naturally occurring sibirinone, (E)-6-(pent-1-en-1-yl)-2H-pyran-2-one, and (E)-6-(hept-1-en-1-yl)-2H-pyran-2-one.

Microwave- or microreactor-assisted conversion of furfuryl alcohols into 4-hydroxy-2-cyclopentenones

Ulbrich, Kathrin,Kreitmeier, Peter,Reiser, Oliver

, p. 2037 - 2040 (2010)

The conversion of a variety of furfuryl alcohols, derived from renewable non edible resources such as bran, into 4-hydroxy-2-cyclopentenones was accomplished using microwave irradiation. In subcritical water (220° C, 15.5 bar) without the need for any catalyst the reaction proceeds approximately two orders of magnitude faster with up to twice the yield compared to methods previously reported that apply conventional heating techniques. For the parent furfuryl alcohol the process could be transferred to a microreactor, allowing the synthesis of 4-hydroxy-2-cyclopentenone in a continuous flow system on multigram scale. Georg Thieme Verlag Stuttgart · New York.

Progress toward the total synthesis of (±)-havellockate

Beingessner, Rachel L.,Farand, Julie A.,Barriault, Louis

, p. 6337 - 6346 (2010)

Havellockate (1) was isolated from the soft coral Sinularia granosa located on the Havellock island in the Indian Ocean. This highly compact and polyoxygenated marine diterpene bears a cis-fused hydrindane core that contains eight stereogenic centers as well as a spiro-lactone. To the best of our knowledge, no syntheses of 1 have been reported yet. Herein, we describe the synthesis of the all-carbon framework of havellockate (1) in 18 chemical operations. Our approach highlights the efficiency and utility of the hydroxy-directed Diels-Alder (HDDA) reaction to quickly access the cis-fused hydrindane core and securing the correct stereochemistry at C6 and C7. Moreover, six of the eight stereogenic centers have been installed in the correct stereochemistry.

Enzymatic kinetic resolution studies of racemic 4-hydroxycyclopent-2-en- 1-one using Lipozyme IM

Ghorpade, Sandeep R.,Bastawade, Kulbhushan B.,Gokhale, Digambar V.,Shinde, Popat D.,Mahajan, Vishal A.,Kalkote, Uttam R.,Ravindranathan

, p. 4115 - 4122 (1999)

Enzymatic kinetic resolution studies of (±)-4-hydroxycyclopent-2-en-1- one 2 were taken up in organic solvents by transesterification with vinyl acetate and alcoholysis of its acetate 3 as an alternative to the desymmetrization of meso-cyclopentenediol to provide faster and economic access to enantiomerically pure 4-(R)-tert-butyldimethylsilyloxycyclopent-2- en-1-one 1. Parameters were screened using Lipozyme IM as catalyst. Although enantioselectivity observed was moderate (E=24, by alcoholysis of 3 with 2-butanol), trends in the effect of solvent, water content and alcohol structure showed useful directions for screening of other enzymes for optimization of the method to useful levels of efficiency.

Synthesis of 3′-halo-5′-norcarbocyclic nucleoside phosphonates as potent anti-HIV agents

Hamon, Nadège,Kaci, Malika,Uttaro, Jean-Pierre,Périgaud, Christian,Mathé, Christophe

, p. 642 - 654 (2018)

The synthesis and the antiviral evaluation of 3’-halo (iodo and fluoro) 5’-norcarbocyclic nucleoside phosphonates is described. No antiviral activity was observed against Zika virus, Dengue virus 2, HSV-1, HSV-2 and Chikungunya virus. In contrast, some of the synthesized compounds are potent inhibitors of the replication of HIV-1, comparatively to (R)-PMPA, with no concomitant cytotoxicity.

4-Heterosubstituted Cyclopentenone Antiviral Compounds: Synthesis, Mechanism, and Antiviral Evaluation

Mantione, Daniele,Aizpuru, Olatz Olaizola,Memeo, Misal Giuseppe,Bovio, Bruna,Quadrelli, Paolo

, p. 983 - 991 (2016)

Racemic 4-oxocyclopent-2-en-1-yl acetate was used in a short synthesis of nucleoside analogues with pyrimidine and purine heterobases. The protocol is based on a typical nucleophilic substitution process. Uracil, thymine, 6-chloropurine, and some adenines gave the expected 4-heterosubstituted products along with the isomeric 2-heterosubstituted compounds as minor components. Samples of selected products were evaluated for their antiviral activity in a primary screening against a variety of viruses belonging to different classes. One of the compounds was found to be highly active against human papilloma virus (HPV).

Development of the carbocyclic nucleoside MDL 201449A: A tumor necrosis factor-α inhibitor

Watson, Timothy J.N.,Curran, Timothy T.,Hay, David A.,Shah, Ramnik S.,Wenstrup, David L.,Webster, Mark E.

, p. 357 - 365 (1998)

An efficient synthesis of (1S,4R)-(-)-4-tert-butyldimethylsilyloxy-2-cyclopentenyl acetate and (1R,4S)-(-)-4-tert-butyldimethylsilyloxy-2-cyclopentenol is described utilizing a furfuryl alcohol rearrangement, followed by a lithium aluminum hydride reduction with high facial selectivity and an efficient enzymatic resolution with pancreatin. Both of these intermediates were successfully utilized in the preparation of the carbocyclic nucleoside 9N-[(1′R,3′R)-trans-3′-hydroxycyclopentanyl]adenine hydrochloride, an agent which inhibits the formation of tumor necrosis factor-α.

Gill,Rickards

, p. 1539,1540 (1979)

Bio-based synthesis of cyclopentane-1,3-diamine and its application in bifunctional monomers for poly-condensation

Alsters, Paul L.,De Wildeman, Stefaan M. A.,Hadavi, Darya,Han, Peiliang,Mogensen, Siri,Monsegue, Luciano G.,Noordijk, Jurrie,Quaedflieg, Peter J. L. M.,Verzijl, Gerard K. M.,van Slagmaat, Christian A. M. R.

, p. 7100 - 7114 (2021/09/28)

A novel and green route for the synthesis of cyclopentane-1,3-diamine (CPDA) from hemicellulosic feedstock is established in this work. Through many explorations and optimizations, the single successful multi-step synthesis was found to comprise: (1) the Piancatelli rearrangement of furfuryl alcohol to 4-hydroxycyclopent-2-enone (4-HCP), (2) a highly improved isomerization of4-HCPinto cyclopentane-1,3-dione (CPDO) using the Ru Shvo catalyst, (3) conversion ofCPDOinto cyclopentane-1,3-dioxime (CPDX), and (4) a mild oxime hydrogenation ofCPDXover Rh/C to afford the desiredCPDA. In addition, diastereomerically purecis- andtrans-isomers ofCPDAwere reacted with (A) bio-based lactones, and (B) 5-(hydroxymethyl)furfural (HMF) to synthesize novel bifunctional diol monomers with internal amide and imine groups, respectively. Monomer5, derived using γ-valerolactone (GVL), was successfully applied in the synthesis of polyurethanes.

Application of hierarchical pore molecular sieve in preparation process of cyclopentadiene and JP-10 aviation fuel

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Paragraph 0023; 0070-0086, (2021/07/01)

The invention relates to an application of a hierarchical pore molecular sieve in a the preparation process of cyclopentadiene and JP-10 aviation fuel. The hierarchical pore molecular sieve is one or two or more of an H-ZSM-5 molecular sieve, an H-beta molecular sieve, an H-Y molecular sieve, an H-USY molecular sieve, a La-Y molecular sieve and an H-MOR molecular sieve with a hierarchical pore structure, a sulfonated SBA-15 molecular sieve, a sulfonated MCM-41 molecular sieve, a sulfonated Ti-SBA-15 molecular sieve, a sulfonated MCM-41 molecular sieve, a sulfonated Zr-MCM-41 molecular sieve and a sulfonated Zr-SBA-15 molecular sieve; and the hierarchical pore structure comprises micropores and mesopores. The catalyst and the raw materials used in the method are cheap and easy to obtain, the preparation process is simple, and the hierarchical pore molecular sieve has high activity and selectivity for rearrangement reaction of furfuryl alcohol, hydrogenation reaction of hydroxyl cyclopentenone and dehydration reaction. The invention provides a cheap and efficient synthesis method for synthesizing the JP-10 aviation fuel from a lignocellulose-based platform compound furfuryl alcohol.