- Macrolactonization Reactions Driven by a Pentafluorobenzoyl Group**
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Macrolactones constitute a privileged class of natural and synthetic products with a broad range of applications in the fine chemicals and pharmaceutical industry. Despite all the progress made towards their synthesis, notably from seco-acids, a macrolactonization promoter system that is effective, selective, flexible, readily available, and, insofar as possible, compatible with manifold functional groups is still lacking. Herein, we describe a strategy that relies on the formation of a mixed anhydride incorporating a pentafluorophenyl group which, due to its high electronic activation enables a convenient access to macrolactones, macrodiolides and esters with a broad versatility. Kinetic studies and DFT computations were performed to rationalize the reactivity of the pentafluorophenyl group in macrolactonization reactions.
- Ciofini, Ilaria,Force, Guillaume,Leb?uf, David,Mayer, Robert J.,Perfetto, Anna
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supporting information
p. 19843 - 19851
(2021/08/13)
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- Efficient method for the lactonization of ω-hydroxycarboxylic acids with di-2-thienyl carbonate by the promotion of catalytic amounts of DMAP and Hf(OTf)4
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An efficient method for the synthesis of macrolides from ω-hydroxycarboxylic acids is established by using an equimolar amount of di-2-thienyl carbonate (2-DTC) and catalytic amounts of 4-(dimethylamino) pyridine (DMAP) and group 4 metal triflates such as hafnium(IV) trifluoromethanesulfonate (Hf(OTf)4). Copyright
- Oohashi, Yoshiaki,Fukumoto, Kentarou,Mukaiyama, Teruaki
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p. 710 - 711
(2007/10/03)
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- A new method for the synthesis of carboxylic esters and lactones with di-2-thienyl carbonate (2-DTC) by the promotion of DMAP and iodine
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The esterification of carboxylic acids with alcohols by using di-2-thienyl carbonate (2-DTC) in the presence of a catalytic amount of 4-(dimethylamino) pyridine (DMAP) proceeded smoothly to afford the corresponding esters in good-to-high yields along with 2(5H)-thiophenone. This esterification was accelerated by the addition of an equimolar amount of iodine to afford the esters in higher yields within a shorter reaction time. Further, cyclization of ω-hydroxycarboxylic acids with an equimolar amount of 2-DTC in the presence of a catalytic amount of DMAP, followed by the addition of 1-4 equimolar amounts of iodine, afforded the corresponding lactones in good-to-high yields under mild conditions. This method was successfully employed in the synthesis of erythro-aleuritic acid lactone.
- Oohashi, Yoshiaki,Fukumoto, Kentarou,Mukaiyama, Teruaki
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p. 1508 - 1519
(2007/10/03)
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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
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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
- Oohashi, Yoshiaki,Fukumoto, Kentarou,Mukaiyama, Teruaki
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- An Effective Use of Benzoic Anhydride and Its Derivatives for the Synthesis of Carboxylic Esters and Lactones: A Powerful and Convenient Mixed Anhydride Method Promoted by Basic Catalysts
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Various carboxylic esters are obtained at room temperature in excellent yields with high chemoselectivities from nearly equimolar amounts of carboxylic acids and alcohols using 2-methyl-6-nitrobenzoic anhydride with triethylamine by the promotion of a basic catalyst such as 4-(dimethylamino)pyridine. A variety of lactones are also prepared in high yields at room temperature from the corresponding ω-hydroxycarboxylic acids with use of 2-methyl-6-nitrobenzoic anhydride in the presence of 4-(dimethylamino)pyridine. A similar reaction 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 are successfully applied to the synthesis of erythro-aleuritic acid lactone and an eight-membered-ring lactone moiety of octalactins A and B. The efficiency of the cyclizations is compared to those of other reported lactonizations.
- Shiina, Isamu,Kubota, Mari,Oshiumi, Hiromi,Hashizume, Minako
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p. 1822 - 1830
(2007/10/03)
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- An effective method for the synthesis of carboxylic esters and lactones using substituted benzoic anhydrides with Lewis acid catalysts
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An efficient mixed-anhydride method for the synthesis of carboxylic esters and lactones using benzoic anhydride having electron withdrawing substituent(s) is developed by the promotion of Lewis acid catalysts. In the presence of a catalytic amount of TiCl2(ClO4)2, various carboxylic esters are prepared in high yields through the formation of the corresponding mixed-anhydrides from 3,5-bis(trifluoromethyl)benzoic anhydride and carboxylic acids. The combined catalyst consisting of TiCl 2(ClO4)2 together with chlorotrimethylsilane functions as an effective catalyst for the synthesis of carboxylic esters from free carboxylic acids and alcohols with 4-(trifluoromethyl)benzoic anhydride. Various macrolactones are prepared from the free ω-hydroxycarboxylic acids by the combined use of 4-(trifluoromethyl)benzoic anhydride and titanium(IV) catalysts together with chlorotrimethylsilane under mild reaction conditions. The lactonization of trimethylsilyl ω-(trimethylsiloxy) carboxylates using 4-(trifluoromethyl)benzoic anhydride is also promoted at room temperature in the presence of a catalytic amount of TiCl 2(ClO4)2. An 8-membered ring lactone, a synthetic intermediate of cephalosporolide D, is successfully synthesized according to this mixed-anhydride method using 4-(trifluoromethyl)benzoic anhydride by the promotion of a catalytic amount of Hf(OTf)4.
- Shiina, Isamu
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p. 1587 - 1599
(2007/10/03)
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- A novel and efficient macrolactonization of ω-hydroxycarboxylic acids using 2-methyl-6-nitrobenzoic anhydride (MNBA)
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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.
- Shiina, Isamu,Kubota, Mari,Ibuka, Ryoutarou
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p. 7535 - 7539
(2007/10/03)
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- A new method for the polymer-supported synthesis of cyclic oligoesters for potential applications in macrocyclic lactone synthesis and combinatorial chemistry
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Attachment of ω-hydroxyalkanecarboxylic acids to Merrifield beads followed by treatment with a catalytic amount of di-n-butyltin oxide in chlorobenzene at 133 °C for 4-18 h brought about the formation of the corresponding cyclic oligomers (COs) as the mai
- Ruddick, Clare L.,Hodge, Philip,Cook, Anthony,McRiner, Andrew J.
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p. 629 - 637
(2007/10/03)
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- An improved and novel approach to macrolactonisation using di-tert-butyl dicarbonate
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A new, facile, mild and simple method for the synthesis of macrolides was achieved from ω- hydroxy acids using di-tertbutyl dicarbonate (Boc2O), a cheap and commercially available reagent. A wide range of substrates were tested and give good yield of lactones. The effect of various simple bases on the yield of the macrolactonisation reaction was also studied.
- Nagarajan,Satish Kumar,Venkateswara Rao
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p. 12349 - 12360
(2007/10/03)
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- Scandium trifluoromethanesulfonate as an extremely active Lewis acid catalyst in acylation of alcohols with acid anhydrides and mixed anhydrides
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Scandium trifluoromethanesulfonate (triflate), which is commercially available, is a practical and useful Lewis acid catalyst for acylation of alcohols with acid anhydrides or the esterification of alcohols by carboxylic acids in the presence of p-nitrobenzoic anhydrides. The remarkably high catalytic activity of scandium triflate can be used for assisting the acylation by acid anhydrides of not only primary alcohols but also sterically-hindered secondary or tertiary alcohols. The method presented is especially effective for selective macrolactonization of ω-hydroxy carboxylic acids.
- Ishihara, Kazuaki,Kubota, Manabu,Kurihara, Hideki,Yamamoto, Hisashi
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p. 4560 - 4567
(2007/10/03)
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- A Novel Method for the Preparation of Macrolides from ω-Hydroxycarboxylic Acids
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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.
- Shiina, Isamu,Mukaiyama, Teruaki
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p. 677 - 680
(2007/10/02)
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- A New Synthetic Method of Macrocyclic Lactones from ω-Iodoalkylacrylates
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When the photostimulated cyclization reaction of ω-iodoalkylacrylates was performed in the presence of metal hydride complexes such as sodium cyanoborohydride (NaBH3CN), sodium borohydride (NaBH4) and potassium borohydride (KBH4), the corresponding macrocyclic lactones were produced.The use of NaBH3CN led to the highest yield of lactones.
- Abe, Motoji,Hayashikoshi, Takaoki,Kurata, Takeo
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p. 1789 - 1792
(2007/10/02)
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- Tin(IV)-catalyzed lactonization of ω-hydroxy trifluoroethyl esters
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1,1,1-Trifluoroethyl esters of ω-hydroxycarboxylic acids were prepared and their conversion to macrocyclic lactones, including ricinelaidic lactone, was studied in the presence of catalytic quantities of tin(IV) reagents; a mechanism involving exchange of alkoxytrialkyltin species is proposed.
- White,Green,Fleming
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p. 3515 - 3518
(2007/10/02)
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- Selective Macrolactonization using Zeolite Molecular Sieves
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'In-pore' reactions of 15-hydroxypentadecanoic acid on dealuminated HY zeolite effected intramolecular esterification exclusively to give the monomeric lactone, pentadecanolide.
- Tatsumi, Takashi,Sakashita, Haru,Asano, Keiko
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p. 1264 - 1265
(2007/10/02)
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- Facile Synthesis of Lactones from Silyl ω-Siloxycarboxylates Using p-Trifluoromethylbenzoic Anhydride and a Catalytic Amount of Active Lewis Acid
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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.
- Mukaiyama, Teruaki,Izumi, Jun,Miyashita, Mitsutomo,Shiina, Isamu
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p. 907 - 910
(2007/10/02)
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- LIPASE CATALYZED SYNTHESIS OF MACROCYCLIC LACTONES IN ORGANIC SOLVENTS
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A new method for the preparation of macrocyclic lactones from ω-hydroxyacid methyl esters is described.The approach utilizes intramolecular transesterification catalyzed by lipase in organic solvents.The procedure is also applicable to the synthesis of asymmetric lactones.
- Makita, Atushi,Nihira, Takuya,Yamada, Yasuhiro
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p. 805 - 808
(2007/10/02)
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- Preparation of Macrocyclic Lactones by Ring Closure of Cesium Carboxylates
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A series of ω-halo fatty acids, the longest being 16-iodohexadecanoic acid, was prepared by oxidation of the corresponding ketones with m-chloroperbenzoic acid in boiling chloroform, followed by ring opening usually with hydrogen iodide in acetic acid at 100 deg C.Solutions of these acids in dimethylformamide (DMF) at concentrations of 5E-3 - 5E-2 M were treated with an equivalent amount of dry Cs2CO3.The solutions were stirred at 40 deg C overnight.Workup of the reaction mixture produced a mixture of (macro)cyclic lactone (macrolide) and its dimer (dilide).For the case of 16-iodohexanoic acid the lactone was isolated in 85percent yield.Yields for other large ring macrolides were also excellent.It was demonstrated that substitution by carboxylate on a secondary halide also goes well to afford the corresponding macrolide with no detectable amount of elimination.The effects of ring size, concentration, and solvent on the ring closure of the cesium carboxylates formed in situ were investigated.DMF is the best solvent of those investigated for the ring closure.Cesium carboxylates also undergo more readily ring closure and in far better yield than the carboxylates of lithium, sodium, potassium, rubidium, silver, thallium, magnesium, strontium, or barium.The S-lactone of ricinelaidic acid was prepared optically pure in 80percent yield from optically pure mesylate of R-ricinelaidic acid, which was treated with cesium carbonate in dry DMF.This demonstrates that the ring closure proceeds with the anticipated SN2 inversion at the hydroxyl-bearing carbon atom.With the same approach optically pure S-zearalenone was protected and subjected to ring opening, and the hydroxyl group was activated as mesylate.Some racemization was found to occur in the ring-opening step.On treatment of this material with dry cesium carbonate in DMF, the desired ring closure took place in 80percent yield to provide an excess of the protected R enantiomer of zearalenone.On the basis of these results, some speculations are made concerning the action of cesium in promoting ring closure to macrocyclic lactones.
- Kruizinga, Wim H.,Kellogg, Richard M.
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p. 5183 - 5189
(2007/10/02)
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- Effect of Inverse Micelles on the Competition between Lactonization and Polymerization Reactions of an ω-Hydroxy Carboxylic Acid
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The ability of inverse micelles to influence the competition between carbodiimide-mediated lactonization and polymerization of 15-hydroxypentadecanoic acid (1), yielding pentadecanolide (2) and polymer (3), respectively, has been investigated by using inverse micellar systems in benzene based on di-n-dodecyldimethylammonium bromide (DDABr) and on bis(2-ethylhexyl) sodium sulfosuccinate (AOT) with and without water pools.Two ionic carbodiimides, 1-cyclohexyl-3-carbodiimide p-toluenesulfonate (4) and 1--3-ethylcarbodiimide hydrochloride (5), were used.The inherent ability of carbodiimide 4 to effect lactonization of 1 is inhibited moderately by DDABr inverse micelles without water pools and completely by AOT inverse micelles without water pools.Carbodiimide 4 did not effect esterification when these inverse micellar systems contained water pools; carbodiimide 5 apparently did not do so under any of the conditions used.
- Jaeger, David A.,Ippoliti, J. Thomas
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p. 4964 - 4968
(2007/10/02)
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