64550-47-6Relevant articles and documents
Characterization of novel isobenzofuranones by DFT calculations and 2D NMR analysis
Teixeira, Milena G.,Alvarenga, Elson S.
, p. 623 - 631 (2016/08/26)
Phthalides are frequently found in naturally occurring substances and exhibit a broad spectrum of biological activities. In the search for compounds with insecticidal activity, phthalides have been used as versatile building blocks for the syntheses of novel potential agrochemicals. In our work, the Diels–Alder reaction between furan-2(5H)-one and cyclopentadiene was used successfully to obtain (3aR,4S,7R,7aS)-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1(3H)-one and (3aS,4R,7S,7aR)-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1(3H)-one (2) and (3aS,4S,7R,7aR)-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1(3H)-one and (3aR,4R,7S,7aS)-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1(3H)-one (3). The endo adduct (2) was brominated to afford (3aR,4R,5R,7R,7aS,8R)-5,8-dibromohexahydro-4,7-methanoisobenzofuran-1(3H)-one and (3aS,4S,5S,7S,7aR,8S)-5,8-dibromohexahydro-4,7-methanoisobenzofuran-1(3H)-one (4) and (3aS,4R,5R,6S,7S,7aR)-5,6-dibromohexahydro-4,7-methanoisobenzofuran-1(3H)-one and (3aR,4S,5S,6R,7R,7aS)-5,6-dibromohexahydro-4,7-methanoisobenzofuran-1(3H)-one (5). Following the initial analysis of the NMR spectra and the proposed two novel unforeseen products, we have decided to fully analyze the classical and non-classical assay structures with the aid of computational calculations. Computation to predict the 13C and 1H chemical shifts for mean absolute error analyses have been carried out by gauge-including atomic orbital method at M06-2X/6-31+G(d,p) and B3LYP/6-311+G(2d,p) levels of theory for all viable conformers. Characterization of the novel unforeseen compounds (4) and (5) were not possible by employing only the experimental NMR data; however, a more conclusive structural identification was performed by comparing the experimental and theoretical 1H and 13C chemical shifts by mean absolute error and DP4 probability analyses. Copyright
Synthesis and insecticidal activity of lactones derived from furan-2(5H)-one
Teixeira, Milena G.,Alvarenga, Elson S.,Pimentel, Mirian F.,Pican?o, Marcelo C.
, p. 2279 - 2289 (2015/11/10)
Ten 4,7-methanoisobenzofuran-1(3H)-ones were synthesized and their insecticidal activities against the insect pest Diaphania hyalinata were evaluated. The most active substances have been selected from the initial screening to find the dose to kill 50 (LD50) and 90percent (LD90) of the melonworm. Time-mortality curves of the three selected formulations at the LD90 concentration have been made against D. hyalinata. From the time-mortality curves we found that the formulation (3aR,4R,5S,6S,7S,7aS)- and (3aS,4S,5R,6R,7R,7aR)-5,6-dichlorohexahydro-4,7-methanoisobenzofuran-1(3H)-one + (3aR,4R,5R,6R,7S,7aS)- and (3aS,4S,5S,6S,7R,7aR)-5,6-dichlorohexahydro-4,7-methanoisobenzofuran-1(3H)-one has killed 50percent of the melonworm after 2 h, presenting the best knockdown effect. Bioassays against Solenopsis saevissima and Tetragonisca angustula were carried out for the lactones selected in the initial screening against D. hyalinata. The formulation (3aS,4R,5S,6S,7S,7aR)- and (3aR,4S,5R,6R,7R,7aS)-5,6-dibromohexahydro-4,7-methanoisobenzofuran-1(3H)-one + (3aS,4R,5R,6R,7S,7aR)- and (3aR,4S,5S,6S,7R,7aS)-5,6-dibromohexahydro-4,7-methanoisobenzofuran-1(3H)-one has killed 31.25 and 68.30percent of the pest natural enemy and the pollinator bee, respectively. At the same concentration this formulation killed 90percent of D. hyalinata. The selectivity in favor of the non-target organisms has rendered this formulation a position as a promising agrochemical.
Microbial alcohol dehydrogenase screening for enantiopure lactone synthesis: Down-stream process from microtiter plate to bench bioreactor
Boratyński,Pannek,Walczak,Janik-Polanowicz,Huszcza,Szczepańska,Martinez-Rojas,Olejniczak
, p. 1637 - 1646 (2015/02/05)
One-pot conversion with whole cells of bacteria was performed for biooxidation of meso monocyclic (3a-b) and bicyclic diols (3c-e) into corresponding chiral lactones of bicyclo[4.3.0]nonane structure (2a-b) as well as exo- and endo-bridged lactones with the structure of [2.2.1] (3c-d) and [2.2.2] (3e). Micrococcus sp. DSM 30771 was selected as biocatalyst with significant alcohol dehydrogenase activity. Among tested strains, microbial oxidation of meso diols 3a-e catalyzed by Micrococcus sp. afforded enantiomerically pure ((+)-(2S,3R)-2c (ee = 99%), (+)-(2S,3R)-2e (ee = 99%)) or enriched ((+)-(1S,5R)-2a (ee = 90%), (-)-(1S,5R)-2b (ee = 86%), (+)-(2S,3R)-2d (ee = 80%)) lactone moieties. Comparative study with respect to microbial cultivation as well as biooxidation was undertaken to verify agreement of secondary metabolite biosynthesis in different scales: from MTP (4 mL), across shake flask (100 mL) till bioreactor (4 L). The results from biotransformations showed quite similar dependence in oxidation of all substrates 3a-e in MTP and flasks as well, thereby confirmed the validity and reasonable approach of using MTP for preliminary studies.
A Diels-Alder/retro-Diels-Alder approach for the enantioselective synthesis of microbial butenolides
Citron, Christian A.,Wickel, Susanne M.,Schulz, Barbara,Draeger, Siegfried,Dickschat, Jeroen S.
, p. 6636 - 6646 (2013/01/15)
Several volatile lactones have been identified from the endophytic fungus Geniculosporium sp. isolated from the rockrose Cistus monspeliensis, commonly known as Montpelier cistus. The fungal volatiles were collected from agar-plate cultures by using a closed-loop stripping apparatus and the headspace extracts were analysed by GC-MS. Structures for these lactones were proposed from their mass spectral data. The suggested structures were verified by synthesis of reference compounds through a Diels-Alder/retro-Diels-Alder approach. This synthetic method was also successfully applied in the synthesis of butenolides that are signalling molecules from streptomycetes. For the enantioselective synthesis of these butenolides a modified route including an enantioselective Diels-Alder reaction was used.
Dimethylaluminum methide complex Tf2CHAlMe2: an effective catalyst for Diels-Alder reaction of α,β-unsaturated lactone derivatives with cyclopentadiene
Yanai, Hikaru,Takahashi, Arata,Taguchi, Takeo
, p. 12149 - 12159 (2008/02/10)
Lewis acid derived by mixing Tf2CH2 and Me3Al was found to be an effective catalyst system for the catalytic DA reaction of less reactive α,β-unsaturated lactone derivative with cyclopentadiene (CP). In this catalyst system, Tf2CHAlMe2 is an active species and an excess amount of Me3Al plays an important role to lower the catalyst loading. Substituent effect of the lactone framework on π-facial selectivity was also examined. In the reactions of both γ-substituted 5-membered lactone derivatives and γ- or δ-methylated 6-membered lactone derivatives with CP, selective attack on the anti face of γ- or δ-substituent was observed. On the other hand, in the cases of γ- or ε-methylated 7-membered lactone derivatives, CP favorably attacked on the syn face.
An efficient oxidative lactonization of 1,4-diols catalyzed by Cp*Ru(PN) complexes
Ito, Masato,Osaku, Akihide,Shiibashi, Akira,Ikariya, Takao
, p. 1821 - 1824 (2008/02/02)
An efficient oxidative lactonization of 1,4-diols in acetone is accomplished by the well-defined ruthenium catalyst, whose bifunctional nature underlies the high efficiency as well as unique chemo- and regioselectivity of the reaction which provides a rapid access to γ-butyrolactones including flavor lactones hinokinin, and muricatacin.
Bis-aluminated triflic amide promoted Diels-Alder reactions of α,β-unsaturated lactones
Saito, Akio,Yanai, Hikaru,Taguchi, Takeo
, p. 9439 - 9442 (2007/10/03)
The bis-aluminated triflic amides such as TfN[Al(Me)Cl]2 and TfN[Al(iBu)2]2, which are derived from triflic amide (1 mol) and aluminum reagent (2 mol), can efficiently promote the Diels-Alder reaction of α,β-unsaturated la
Synthesis of 3,11-Dioxatetracyclo[6.3.0.02,6.05,9]undecanes and 3,5,7-Trioxapentacyclo[7.2.1.02,8.04,11.0 6,10]dodecane
Lin, Hui-Chang,Wu, Chung-Yi,Wu, Hsien-Jen
, p. 609 - 616 (2007/10/03)
The synthesis of 3,11-dioxatetracyclo[6.3.0.02,6.05,9]undecanes has been accomplished from furans in a short sequence by iodine-induced cyclization reaction. The application of iodine-induced cyclization reaction for the synthesis of 3,5,7-trioxapentacyclo[7.2.1.02,8.04,11.0 6,10]dodecane itself was also demonstrated.
Synthesis of 3,5,7-Trioxapentacyclo[7.2.1.02,8.04,11.0 6,10]dodecane. A Novel Diacetal Trioxa-Cage
Tsai, Shih-Hwa,Wu, Hsien-Jen,Chung, Wen-Sheng
, p. 445 - 449 (2007/10/03)
3,5,7-Trioxapentacyclo[7.2.1.02,8.04,11.0 6-10]dodecane, the parent compound of novel diacetal trioxacages, was synthesized from maleic anhydride cyclopentadiene adduct 1 by a four-step sequence. Attempts for the synthesis
Enzyme mediated optical resolution of endo-norbornene lactone
Janssen,Klunder,Zwanenburg
, p. 7219 - 7222 (2007/10/02)
The enzymatic resolution of some norbornene esters, -carboxylic acids and -methanols was evaluated. Good results were obtained for the Porcine Pancreatic Lipase (PPL) catalyzed transesterification of norbornene methanols 12 and 13 in methyl acetate. A formal kinetic resolution of endo-norbornene lactone 7 could be achieved through the PPL-catalyzed transesterification of iodolactone 15 in methyl acetate. Both enantiomers of lactone 7 were obtained enantiomerically pure in good overall yields.
