62251-98-3Relevant academic research and scientific papers
Intramolecular 1,6-conjugate addition approach for construction of the hydrindane framework: Total synthesis of (±)-coronafacic acid
Nara, Shinji,Toshima, Hiroaki,Ichihara, Akitami
, p. 6745 - 6748 (1996)
A new approach for the construction of the hydrindane framework has been achieved by intramolecular 1,6-conjugate addition under some basic conditions. The precursors, α, β, γ, δ-unsaturated esters (11a-11d) were synthesized from the ester 8 and acrolein derivatives (6a-6d) via aldol condensation. This methodology was applied to the total synthesis of (±)-coronafacic acid and its analogues.
Syntheses and Potato Tuber-inducing Activity of Coronafacic Acid Analogues
Toshima, Hiroaki,Nara, Shinji,Ichihara, Akitami,Koda, Yasunori,Kikuta, Yoshio
, p. 681 - 688 (1998)
Coronafacic acid (1) is an acid component of coronatine, and has been isolated from several pathovars of Pseudomonas syringae. Syntheses of C6-non- and C6-alkyl-substituted analogues of 1 were accomplished via intramolecular 1,6-conjugate addition as the key step. Among them, 1 and four C6-alkyl-substituted analogues exhibited potato tuber-inducing activity, but the C6-non-substituted analogue did not. It was revealed that a certain length of the C6-alkyl group was necessary to exhibit activity.
Stereoselective Route to Functionalized cis-Hydrindanes from Tricyclo2,6>decan-10-ones. A Total Synthesis of (+/-)-Coronafacic Acid
Mehta, Goverdhan,Praveen, Marapaka
, p. 1573 - 1575 (1993)
A flexible approach to functionalized cis-hydrindanes via Haller-Bauer type cleavage of endo-tricyclo2,6>decan-10-ones is delineated and its efficacy demonstrated through a concise synthesis of (+/-)-coronafacic acid.
Stereoselective Syntheses of all the Possible Stereoisomers of Coronafacic Acid
Hayashi, Kengo,Kato, Nobuki,Kuwahara, Shigefumi,Ogura, Yusuke,Tozawa, Sho,Ueda, Minoru,Watanabe, Raku
, p. 1008 - 1017 (2020)
An efficient and stereoselective syntheses of all the possible stereoisomers of coronafacic acid (CFA) has been developed. The stereochemistries of C3a and C7a were controlled in a diastereoselective Diels-Alder type cycloaddition using a chiral auxiliary. CFA and 6-epi-CFA were synthesized by hydrogenation of a common intermediate. During the synthesis of 6-epi-CFA, we established that its cis-fused configuration is important for the introduction of C4-C5 double bond by dehydration. This report is the first practical synthesis of both 6-epi-CFA, and its enantiomer.
An enantioselective ambimodal cross-Diels–Alder reaction and applications in synthesis
Cai, Quan,Chen, Xiangyang,Houk, K. N.,Lu, Qi-Tao,Tan, Kui,Xu, Meng-Meng,Yang, Limin
, p. 892 - 900 (2021/10/20)
Compared with the conventional Diels–Alder reaction, the development of selective cross-Diels–Alder reactions between two different conjugated dienes, especially in a catalytic asymmetric manner, has been neglected. We now report a peri- and enantioselective cross-Diels–Alder reaction of 3-alkoxycarbonyl-2-pyrones with unactivated conjugated dienes catalysed by a copper(II)–bis(oxazoline) complex, leading to formal inverse-electron-demand adducts with high enantioselectivity under mild reaction conditions. Computational studies showed that this reaction proceeds through an ambimodal transition state: post-transition-state bifurcation leads to [2+4] and [4+2] adducts with the same enantioselectivity, followed by a facile Cope rearrangement to provide a single observed thermodynamic [2+4] product. This reaction occurs with a wide variety of cyclopentadienes, fulvenes and cyclohexadienes, providing a highly efficient and enantioselective approach to densely functionalized cis-bicyclic scaffolds. The synthetic value of this reaction is demonstrated by the asymmetric synthesis of two biologically important natural products, artemisinic acid and coronafacic acid. [Figure not available: see fulltext.].
A scalable synthesis of (+)-coronafacic acid
Kato, Nobuki,Miyagawa, Saki,Nomoto, Haruna,Nakayama, Misuzu,Iwashita, Makoto,Ueda, Minoru
, p. 423 - 430 (2020/02/11)
A facile, efficient, and scalable synthesis of optically pure coronafacic acid by resolution of racemic coronafacic acid obtained using an improved version of Watson's method has been developed. By optimizing the boron-mediated aldol reaction of Watson, we were able to prepare 2.1 g of racemic coronafacic acid. This was coupled with (S)-4-isopropyl-2-oxazolidinone to give a mixture of diastereomeric coronafacyl oxazolidinones, which were readily separable by silica-gel column chromatography to give 630 mg of optically pure (+)-coronafacic acid.
Synthesis of coronafacic acid via TBAF-assisted elimination of the mesylate and its conversion to the isoleucine conjugate
Kosaki, Yusuke,Ogawa, Narihito,Wang, Qian,Kobayashi, Yuichi
supporting information; experimental part, p. 4232 - 4235 (2011/10/09)
An aldol reaction followed by elimination of the derived mesylate was used to construct the side chain that was designed to afford the cyclohexene ring of coronafacic acid via intramolecular alkylation. Elimination of the mesylate proceeded with TBAF. The
Azido-coronatine: A useful platform for "click chemistry"- mediated probe synthesis for bioorganic studies
Okada, Masahiro,Egoshi, Syuusuke,Ueda, Minoru
, p. 2092 - 2095 (2011/06/19)
We report on the development of azide-coronatine as a useful platform for azide alkyne cycloaddition ("click chemistry")-mediated synthesis of molecular probes. (p)-Azido-coronatine was synthesized in 10 steps with 11% yield using improved synthesis of coronafacic acid, in which the highly exo-selective Diels-Alder reaction (endo:exo > 1:25) is the key step. Azido coronatine was as effective as the original coronatine in a stomatal opening assay, and was easily modified to a fluorescein isothiocyanate (FITC)-labeled probe with high yield.
Total syntheses of coronatines by exo-selective Diels-Alder reaction and their biological activities on stomatal opening
Okada, Masahiro,Ito, Satoko,Matsubara, Akira,Iwakura, Izumi,Egoshi, Syusuke,Ueda, Minoru
experimental part, p. 3065 - 3073 (2011/02/25)
The natural phytotoxin coronatine, which is composed of two individual parts, coronafacic acid and coronamic acid, exhibits various promising biological activities similar to jasmonic acid. Interestingly, coronatine induces stomatal opening involving the swelling of guard cells in which jasmonic acid is not involved as an endogenous regulator. We established syntheses of four stereoisomers of coronatine employing the exo-selective Diels-Alder reaction as a key step. Remarkable differences in stomatal opening activity were observed between enantiomers of coronatine. This result strongly suggests that the stereo structure of coronatine is very important for its stomatal opening activity. In addition, SAR studies suggested that coronatine operates as a molecular mimic of jasmonyl-l-isoleucine in plant guard cells.
Expedient stereoselective synthesis of coronafacic acid through intramolecular Diels-Alder cyclization
Moreau, Benoit,Ginisty, Maryon,Alberico, Dino,Charette, Andre B.
, p. 1235 - 1240 (2007/10/03)
(Chemical Equation Presented) A stereoselective synthesis of coronafacic acid, a natural component of the phytotoxin coronatin, was achieved using an intramolecular Diels-Alder reaction as the key step. The triene precursor bearing a substituted diene and a vinylketone as dienophile was synthesized and then tested in the thermal intramolecular cyclization. We have devised a new strategy to assemble the E,Z-diene through the stereoselective aldol reaction of an ester enolate followed by a stereoselective dehydration. Following the thermal cyclization, the corresponding hydrindanone thereby obtained with the desired relative stereochemistry could easily be converted into the natural product. The synthesis of the coronafacic acid was accomplished in six steps in 29% overall yield.
