106-02-5Relevant articles and documents
A Short Synthesis of 15-Pentadecanolide
Stanchev, Stephan,Milenkov, Branimir,Hesse, Manfred
, p. 6107 - 6108 (1993)
15-Pentadecanolide was synthesised by a five step, two pot reaction sequence, starting from 2-nitrocyclododecanone in a 60percent overall yield.
Macrolactonization of hydroxy acids using a polymer bound carbodiimide
Keck,Sanchez,Wager
, p. 8673 - 8676 (2000)
An efficient macrolactonization procedure using a polymer bound carbodiimide is described. The procedure uses the polymer supported reagent as a replacement for dicyclohexylcarbodiimide and thus considerably simplifies the workup for such reactions. Partitioning between macrolactone and diolide is shown to depend upon the equivalents of reagent used in cases for which lactonization is difficult. (C) 2000 Published by Elsevier Science Ltd.
Synthesis of ω-hydroxy carboxylic acids and α,ωdimethyl ketones using α,ω-diols as alkylating agents
Iuchi, Yosuke,Hyotanishi, Megumi,Miller, Brittany E.,Maeda, Kensaku,Obora, Yasushi,Ishii, Yasutaka
, p. 1803 - 1806 (2010)
"Chemical equation presented" Synthesis of ω-hydroxy carboxylic acids and α,ω-dimethyl diketones was successfully achieved by using α,ω-diols as alkylating agents under the influence of an iridium catalyst. For example, the alkylation of butyl cyanoacetate with 1,13-tridecanediol in the presence of [IrCl(cod)]2 or [rrCl(coe) 2]2 gave rise to butyl 2-cyano-15-hydroxypentadecanoate in good yield which is easily converted to cyclopentadecanolide (CPDL). In addition, the alkylation of acetone with 1,10-decanediol in the presence of [IrCl(cod)]2 and KOH resulted in an important muscone precursor, 2,15-hexadecanedione (HDDO), in good yield.
Cyanuric chloride, a useful reagent for macrocyclic lactonization
Venkataraman,Wagle
, p. 1893 - 1896 (1980)
Six ω-hydroxy acids have been converted to macrocyclic lactones by treatment with cyanuric chloride and triethylamine in acetone at room temperature. The mechanism apparently involves activation of both the carboxyl and hydroxyl groups.
A novel and efficient macrolactonization of ω-hydroxycarboxylic acids using 2-methyl-6-nitrobenzoic anhydride (MNBA)
Shiina, Isamu,Kubota, Mari,Ibuka, Ryoutarou
, p. 7535 - 7539 (2002)
A variety of lactones were prepared in high yields at room temperature from the corresponding ω-hydroxycarboxylic acids using 2-methyl-6-nitrobenzoic anhydride in the presence of 4-(dimethylamino)pyridine. A similar reaction also occurs with triethylamine when using a catalytic amount of 4-(dimethylamino)pyridine 1-oxide as an effective promoter for the intramolecular condensation reaction. These methods were successfully applied to the synthesis of erythro-aleuritic acid lactone and the efficiency of the cyclizations is compared to those of other reported mixed anhydride methods.
Transition-State-Stabilized Macrolide Closures
Rastetter, William H.,Phillion, Dennis P.
, p. 1535 - 1538 (1980)
Thiol-functionalized crown ethers serve as reagents for macrolide closures.The thioesters derived from these crown ethers and ω-hydroxy carboxylic acids yield macrolides when treated with potassium tert-butoxide.The reaction proceeds via a templated conformation in which the ω-alkoxide is held proximate to the thioester through ionic bonding to the crown-bound potassium cation.Variations in crown ether structure show that the criterion of proximate binding is necessary but not sufficient to ensure efficient macrolide closure.The optimal crown ether reagent provides transition-state stabilization for the attack of the alkoxide on the thioester carbonyl by situating the carbonyl oxygen immediately adjacent to the crown-bound potassium cation.
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Kruizinga,Kellogg
, p. 286 (1979)
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Di-tert-butyl pyrocarbonate mediated synthesis of macrocyclic lactones from ω-hydroxy acids
Nagarajan,Kumar, V. Satish,Venkateswara Rao
, p. 5835 - 5838 (1997)
A new and facile method for the synthesis of macrocyclic lactones was achieved from ω-hydroxy acids using Di-tert-butyl pyrocarbonate [BOC2O], a cheap and commercially available reagent.
A New Synthesis of Medium and Large Membered Lactones via Denitration of Nitro Lactones
Ono, Noboru,Miyake, Hideyoshi,Kaji, Aritsune
, p. 4997 - 4999 (1984)
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High Dilution via Solid-Liquid Phase-Transfer Catalysis. A Practical Approach to the Synthesis of Macrolides
Kimura, Yoshikazu,Regen, Steven L.
, p. 1533 - 1534 (1983)
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SmI2-Promoted conjugate reduction of α,β-unsaturated esters and ketones studied in comparison with Mukaiyama-Michael reaction of ketene silyl acetal
Fujita, Yukihiro,Fukuzumi, Shunichi,Otera, Junzo
, p. 2121 - 2124 (1997)
SmI2-promoted conjugate reduction of α,β-unsaturated esters and ketones proceeds in a manner quite similar to Mukaiyama-Michael reaction of ketene silyl acetal. The more substituted eaters are reduced more preferentially than the less substituted ones. The substrates with a 12 or 16 membered-ring structure undergo reduction smoothly. On the other hand, the 6-membered substrates completely fail to react under the same conditions. These results indicate generation of intermediate enolate radicals to be a key step for the conjugate reduction.
Conformationally unbiased macrocyclization reactions by ring closing metathesis
Fuerstner, Alois,Langemann, Klaus
, p. 3942 - 3943 (1996)
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Selective Macrolactonization using Zeolite Molecular Sieves
Tatsumi, Takashi,Sakashita, Haru,Asano, Keiko
, p. 1264 - 1265 (1993)
'In-pore' reactions of 15-hydroxypentadecanoic acid on dealuminated HY zeolite effected intramolecular esterification exclusively to give the monomeric lactone, pentadecanolide.
A Novel Method for the Preparation of Macrolides from ω-Hydroxycarboxylic Acids
Shiina, Isamu,Mukaiyama, Teruaki
, p. 677 - 680 (1994)
An efficient method for the synthesis of macrolides directly from ω-hydroxycarboxylic acids is established by using 4-(trifluoromethyl)benzoic anhydride and a catalytic amount of active titanium(IV) salts together with chlorotrimethylsilane under mild conditions.
Ring-expansion reaction of 1-hydroperoxy-16-oxabicyclo[10.4.0]hexadecane catalyzed by copper ions: Use in the synthesis of 15-pentadecanolide
Ogibin,Terent'ev,Nikishin
, p. 1166 - 1169 (1998)
A catalytic procedure has been developed for the synthesis of 15-pentadecanolide (1) from readily available 1-hydroperoxy-16-oxabicyclo[10.4.0]hexadecane (2). The method is based on the reaction of hydroperoxide 2 with copper acetate (0.15-5 mol.%). Ring expansion occurred as a result of generation of tertiary bicyclohexadecyloxyl radicals 4 from hydroperoxide 2 under the action of CuI ions, β-scission of the radicals accompanied by regioselective cleavage of the bridge bond to form macrocyclic C-centered radicals 5, and their oxidation by CuII ions to (E)-11- and (E)-12-pentadecen-15-olides (6). The products obtained were converted into 15-pentadecanolide by subsequent catalytic hydrogenation over a Pd catalyst in a yield of more than 90% with respect to hydroperoxide 2.
N-NITROSATION AND N-NITRATION OF LACTAMS. FROM MACROLACTAMS TO MACROLACTONES
Torra, Nuria,Urpi, Felix,Vilarrasa, Jaume
, p. 863 - 868 (1989)
N-Nitroso and N-nitro derivatives of lactams, from 2-pyrrolidinone to 15-pentadecanelactam, have been characterized by 1H NMR, 13C NMR, and IR spectroscopy.The conversion of these nitrosolactams and nitrolactams to lactones has been systematically (re)investigated.
Facile Synthesis of Lactones from Silyl ω-Siloxycarboxylates Using p-Trifluoromethylbenzoic Anhydride and a Catalytic Amount of Active Lewis Acid
Mukaiyama, Teruaki,Izumi, Jun,Miyashita, Mitsutomo,Shiina, Isamu
, p. 907 - 910 (1993)
The lactonization of silyl ω-siloxycarboxylates is successfully carried out under mild conditions in good to high yields by using p-trifluoromethylbenzoic anhydride and a catalytic amount of active acidic species generated in situ from TiCl4 and AgClO4.
Direct macrolactonization of seco acids via hafnium(IV) catalysis
De Léséleuc, Mylene,Collins, Shawn K.
, p. 1462 - 1467 (2015)
Efficient direct macrolactonization of seco acids can be catalyzed by Hf(OTf)4 in high yields, forming water as the sole byproduct. The Hf(OTf)4 catalyst possesses unique reactivity characteristics relative to other Lewis acids, as it promotes macrolactonization over hydrolysis even in the presence of excess water. In addition to forming a variety of macrolactones and benzolactones (55-90%), intermolecular direct esterifications of carboxylic acids and alcohols were also possible and demonstrated compatibility with common carbamate, silyl ether, alkoxymethyl ether, and acetal protecting groups. All of the macrolactonization and esterification processes developed are operationally simple, "one-pot" reactions that exploit a commercially available catalyst without the need for slow addition or azeotropic techniques.
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Stoll,Rouve
, (1935)
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A new method for the lactonization of ω-hydroxy carboxylic acids with Di-2-thienyl carbonate by the promotion of DMAP and iodine
Oohashi, Yoshiaki,Fukumoto, Kentarou,Mukaiyama, Teruaki
, p. 72 - 73 (2005)
Successive reactions of ω-hydroxycarboxylic acids with an equimolar amount of di-2-thienyl carbonate (2-DTC) in the presence of a catalytic amount of 4-(dimethylamino)pyridine (DMAP) followed by an addition of 2-4 equimolar amounts of iodine afforded the corresponding lactones in good to high yields. Copyright
Proton-transfer Steps in Steglich Esterification: A Very Practical New Method for Macrolactonization
Boden, Eugene P.,Keck, Gary E.
, p. 2394 - 2395 (1985)
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Highly selective macrocyclic ring-closing metathesis of terminal olefins in non-chlorinated solvents at low dilution
Dumas, Adrien,Colombel-Rouen, Sophie,Curbet, Idriss,Forcher, Gwénael,Tripoteau, Fabien,Caijo, Frédéric,Queval, Pierre,Rouen, Mathieu,Baslé, Olivier,Mauduit, Marc
, p. 436 - 443 (2019)
A set of new ruthenium-indenylidene complexes bearing two unsymmetrical unsaturated N-cycloalkyl-NHC ligands were synthesized. These catalysts proved to be highly selective in the macrocyclic ring-closing metathesis performed in non-chlorinated solvents at low dilution (0.01 M). Without the requirement of benzoquinone derivatives to prevent the isomerisation side reactions, this environmentally friendly catalytic process promoted the synthesis of macrocyclic odorant molecules with remarkable >99% purity.
Highly Substrate-Selective Macrocyclic Ring Closing Metathesis
Lemcoff, N. Gabriel,Nechmad, Noy B.,Phatake, Ravindra S.,Reany, Ofer
supporting information, (2022/03/08)
A selective ring-closing metathesis (RCM) reaction for the formation of large macrocycles by using latent sulfur chelated ruthenium iodide benzylidenes, readily activated by thermal and photochemical (UV-A and visible light) stimuli, is reported. For dienes having one terminal alkene and one internal double bond, the specific affinity of diiodo ruthenium alkylidenes for the unhindered terminus, combined with their reluctance to react with internal olefins, favors RCM over oligomerization, providing high macrocyclic yields even at relatively high concentrations. Alternatively, for substrates containing two internal double bonds, a sacrificial methylene donor can be used to obtain the desired products. With this methodology, lactones, lactams, and macrocyclic ketones ranging from 13- to 22-membered rings could be synthesized in moderate to high yields. In addition, synthetic applications for a one-pot cyclization/reduction sequence to produce Exaltolide, a natural macrolide (commercial musk), Dihydrocivetone, and other saturated macrocycles have been explored. Thus, we disclose herein an important advantage for diiodo ruthenium benzylidene catalysts over their less selective dichloro counterparts and provide a more profound understanding of the mechanisms that provide the enhanced cyclization outcome. (Figure presented.).
Ynamide-Mediated Macrolactonization
Wang, Xuewei,Yang, Ming,Zhao, Junfeng
, p. 5230 - 5235 (2020/05/27)
Macrolactonization represents a long-standing challenge for organic chemists. Herein, an ynamide-mediated macrolactonization of seco-acids with the assistance of an acid catalyst is described. Various macrolactones ranging in ring size from medium to large can be prepared by using this method. The notorious issues associated with conventional macrolactonization reactions, such as the racemization/epimerization of seco-acids containing an α-chirality center, and the E/Z isomerization of α,β-unsaturated seco-acids can be avoided using this method. In addition, the ynamide-mediated two-step macrolactonization reaction can be performed in a one-pot manner, thus offering a user-friendly protocol. Cyclodepsipeptides containing both amide and ester bonds can also be constructed using this method as the key step to facilitate the ring closure. The total synthesis of dehydroxy LI-F04a, which contains a cyclic hexadepsipeptide core, has been accomplished using this method.
