488-10-8Relevant articles and documents
1,2-Bisanionic coupling approach to 2,3-disubstituted cyclopentenols and cyclopentenones
Luparia, Marco,Vadala, Alessandro,Zanoni, Giuseppe,Vidari, Giovanni
, p. 2147 - 2150 (2006)
We describe a new approach to 2,3-disubstituted cyclopentenols and cyclopentenones through two consecutive regioselective additions of equal or different electrophiles to a cyclopentene bisanionic synthon. Indeed, on exposure to BuLi, 3-bromo-2-iodocyclopent-2-enol O-TBS ether undergoes iodine-lithium permutation with complete regioselectivity. Successive reaction of the monolithium anion with different C(sp2)- and C(sp 3)-electrophiles affords the corresponding 2-substituted-3- bromocyclopentenol derivative. Subsequent bromo-lithium exchange with t-BuLi, followed by reaction with an equal or different electrophile, affords the desired 2,3-disubstituted cyclopentenol.
Synthesis of Pyrethroids and Jasmonoids through Palladium-Catalyzed Cross-Coupling Reactions
Heguaburu, Viviana,Pandolfi, Enrique,Parpal, Florencia,Paullier, Ana Paula
, (2022/03/27)
The synthesis of jasmone and related jasmonoids and pyrethroids is described. These compounds play a defensive role in plants and share a common cyclopentenone core with variations in the side chains. Jasmone, cinerone, allylrethrone, and derivatives were synthesized through -allyl palladium cross-coupling of stannane derivatives. With selective hydrogenation, dihydrojasmone, and dihydrocinerone were also synthesized.
Synthesis of Diketones, Ketoesters, and Tetraketones by Electrochemical Oxidative Decarboxylation of Malonic Acid Derivatives: Application to the Synthesis of cis-Jasmone
Ma, Xiaofeng,Dewez, Damien F.,Du, Le,Luo, Xiya,Markó, István E.,Lam, Kevin
, (2018/10/15)
Disubstituted malonic acid derivatives are smoothly converted into diketones and ketoesters in good to excellent yield (68% to 91%) under electrochemical conditions. The scope can be extended to transform trisubstituted bis-malonic acids into tetraketones in 77% to 86% yield. The new method was applied to the total synthesis of cis-jasmone.
Synthesis of Diketones, Ketoesters, and Tetraketones by Electrochemical Oxidative Decarboxylation of Malonic Acid Derivatives: Application to the Synthesis of cis-Jasmone
Ma, Xiaofeng,Du, Le,Luo, Xiya,Markó, István E.,Dewez, Damien F.,Lam, Kevin
, p. 12044 - 12055 (2019/03/01)
Disubstituted malonic acid derivatives are smoothly converted into diketones and ketoesters in good to excellent yield (68% to 91%) under electrochemical conditions. The scope can be extended to transform trisubstituted bis-malonic acids into tetraketones in 77% to 86% yield. The new method was applied to the total synthesis of cis-jasmone.
Ti-Crossed-Claisen condensation between carboxylic esters and acid chlorides or acids: A highly selective and general method for the preparation of various β-keto esters
Misaki, Tomonori,Nagase, Ryohei,Matsumoto, Kunshi,Tanabe, Yoo
, p. 2854 - 2855 (2007/10/03)
Ti-crossed-Claisen condensation between a 1:1 mixture of carboxylic esters and acid chlorides promoted by TiCl4-Bu3N-N-methylimidazole proceeded successfully to give various β-keto esters in good yields with excellent selectivities (19 examples, ～48-95% yield; cross/self-selectivity = ～96/4-99/1). The present method was extended to the condensation between a 1:1 mixture of carboxylic acids and carboxylic esters (six examples, ～70-92% yield; cross/self-selectivity = ～91/9-99/1). To demonstrate the utility of the present two Ti-crossed-Claisen condensations, we performed a couple of efficient short-step syntheses of two natural, representative, and useful perfumes, cis-jasmone and (R)-muscone. Copyright
A three-component coupling approach to cyclopentanoids
Trost,Pinkerton
, p. 7714 - 7722 (2007/10/03)
A new approach to 2,3-disubstituted cyclopentenones has been developed. This approach consists of a two-step protocol involving the cyclization of a Z-vinyl bromide under Barbier type conditions to form a cyclopentenol, which is then oxidatively rearranged to generate the cyclopentenone. The Z-vinyl bromide is in turn derived from a ruthenium catalyzed three-component coupling of an alkyne, an enone, and a HBr equivalent. A range of 2,3-disubstituted cyclopentenones has been generated, including short syntheses of jasmone and dihydrojasmone. Further applicability of this strategy is shown in the total syntheses of tetrahydrodicranenone B, rosaprostol, and a selective COX-2 inhibitor.
Tandem Thermal Reactions for the Synthesis of Jasmonoids
Ho, Tse-Lok,Shyu, Kuo-Feng
, p. 319 - 321 (2007/10/03)
A tandem reaction tactic for the preparation of a jasmonoid intermediate consists of pyrolysis of a spiroannulated cyclopentanone. The thermal decomposition actually involves a retro-Diels-Alder reaction and a homo-1,5-hydrogen shift with cleavage of the cyclopropane unit.
Photoinduced Electron Transfer Reactions of α-Cyclopropyl- And α-Epoxy Ketones. Tandem Fragmentation-Cyclization to Bi-, Tri-, and Spirocyclic Ketones
Kirschberg, Thorsten,Mattay, Jochen
, p. 8885 - 8896 (2007/10/03)
Reductive photoinduced electron transfer (PET) reactions have been performed with various bicyclic a-cyclopropyl-substituted ketones and tertiary amines. The reaction resulted in a regioselective cleavage of one cyclopropyl bond under formation of an exocyclic radical with an endocyclic enolate unit. In the case of bicyclic ketones with an unsaturated side chain, various bicyclic, spirocyclic, and tricyclic products are accessible via radical cyclization, depending on the position of the alkenyl substituent. In addition to triethylamine, W-silylated amines have also been used as electron donors, leading to a variety of compounds, among them are silylated fragmentation products, indicating that a proton is transferred from not only the amine radical cation but also the cationic silyl group. The intramolecular Paternoe-Buechi reaction has also been studied for cyclopropane derivatives of the jasmone type leading to tetracyclic oxetanes. Finally, α-epoxy-substituted ketones have been investigated under PET conditions, yielding ring-opened products.
Cyclopent-2-en-1-ones from [3 + 2]-annulation of 3-ethoxycarbonyl-2-propenylidene(triphenyl)phosphorane and glyoxals: Synthesis of cis-jasmone
Islam, Md. Saiful,Kawano, Tomikazu,Hatanaka, Minoru,Ueda, Ikuo
, p. 5735 - 5738 (2007/10/03)
3-Ethoxycarbonyl-2-propenylidene(triphenyl)phosphorane (2) reacted with glyoxal monohydrates (5) to give 2-substituted 5-ethoxycarbonylcyclopent-2-en-1-ones (6) by [3 + 2]-annulation reaction in the presence of a base. Compounds 6 were easily converted to 2-substituted cyclopent-2-en-1-ones by deethoxycarbonylation. An application of the annulation to synthesis of cis-jasmone is also described.
Synthesis of cis-Jasmone
Tsukasa, Hidetaka
, p. 1181 - 1182 (2007/10/02)
cis-Jasmone 1, an important olfactive ingredient of jasmine flower oil, was synthesized by starting from methyl 3-formylpropionate 2 in a 24 percent overall yield in 7 steps.
