- Stereoselective synthesis of a chiral synthon, 2,2,5-trisubstituted tetrahydropyran, based on simultaneous 1,3- and 1,6-asymmetric induction via nucleophilic acetal cleavage reaction of the bicyclic acetal: A total synthesis of (-)-malyngolide
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A chiral 2,2,5-trisubstituted tetrahydropyran is synthesised efficiently via facial and group selective nucleophilic acetal cleavage reaction of a bicyclic acetal, wherein simultaneous 1,3- and 1,6-asymmetric induction from a sulfinyl chirality is accompl
- Maezaki, Naoyoshi,Matsumori, Yuki,Shogaki, Takeshi,Soejima, Motohiro,Tanaka, Tetsuaki,Ohishi, Hirofumi,Iwata, Chuzo
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- Stereoselective synthesis of marine antibiotic (-)-malyngolide and its stereoisomers.
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A convenient synthetic method for the marine antibiotic (-)-malyngolide and its stereoisomers was accomplished from a chiral alpha-alkoxyketone (4), which was readily available as a chiron. Chiral quaternary carbon synthons (5a) and (5b) as the key intermediates were constructed by the chelation controlled addition of Grignard reagent to 4. The diastereomeric mixture of 5a and 5b was readily transformed into a separable mixture of lactones (7a) and (7b), each of which could be easily separated by silica-gel column chromatography. (-)-Malyngolide and its three stereoisomers were obtained in optically pure form without the need for optical resolution.
- Ichimoto,Machiya,Kirihata,Ueda
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- Novel Synthesis of (-)-Malyngolide using Reactions of Alkylidene Carbenes
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(-)-Malyngolide has been synthesized using three different reactions of alkylidene carbenes, generated by alkenation of carbonyl compounds with dimethyl diazomethylphosphonate.
- Ohira, Susumu,Moritani, Masanori,Ida, Takahiro,Yamato, Masatoshi
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- An Enantiocontrolled Synthesis of (-)-Malyngolide
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Enantioselective synthesis of (-)-malyngolide (1) was accomplished by employing diastereoselective addition of nonylmagnesium bromide to the 2-acylfuran derivative (4), followed by a ring transformation of the resulting optically active 2-furylalcohol (5) to give the pyranone derivative (7) as key step.
- Honda, Toshio,Imai, Minako,Keino, Katsuyuki,Tsubuki, Masayoshi
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- Asymmetric hydrogen transfer protocol for a synthesis of (+)-frontalin and (-)-malyngolide
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An insect aggregate pheromone (+)-frontalin and a marine antibiotic (-)- malyngolide, both bearing a quaternary stereogenic center in their molecules, have been synthesized in diastereocontrolled manner by employing a catalytic asymmetric hydrogen transfer reaction as the key step. An inversion protocol allowing enantioconvergent use of the other enantiomeric resolved product has also been devised. (C) 2000 Elsevier Science Ltd.
- Mikie Kanada, Regina,Taniguchi, Takahiko,Ogasawara, Kunio
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- Novel asymmetric syntheses of (-)-malyngolide and (+)-epi-malyngolide
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The diastereo- and enantioselective synthesis of (-)-malyngolide [(S,R)-1], an antibiotic against Mycobacterium smegmatis and Streptococcus pyogenes, using the asymmetric Carroll rearrangement as key step is described. Furthermore, the diastereo- and enantioselective synthesis by double α,α'-alkylation using SAMP/RAMP hydrazone methodology affords the diastereomer (+)-epi-malyngolide [(S,S)-1].
- Enders, Dieter,Knopp, Monika
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- Biocatalytic Approach for the Total Synthesis of (-)-Malyngolide and Its C(5)-Epimer
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An enzymatic approach has been successfully utilized in the total synthesis of (-)-malyngolide and its C(5)-epimer. The required configuration was established by an enzymatic kinetic resolution and Sharpless asymmetric dihydroxylation.
- Srivastava, Nikhil,Subba Reddy, Basi V.
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p. 267 - 272
(2016/05/02)
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- A new asymmetric total synthesis of enantiopure (-)-malyngolide
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A new asymmetric total synthesis of (-)-malyngolide is described. This synthesis is based on the originally developed catalytic asymmetric IMCP reaction; that is, α-diazo-β-keto sulfone (13) was successfully converted to cyclopropane (12) in 92% yield wit
- Miyamoto, Hidetoshi,Iwamoto, Mitsuhiro,Nakada, Masahisa
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- Stereoselective synthesis of (-)-malyngolide, (+)-malyngolide and (+)-tanikolide using ring-closing metathesis
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The stereoselective syntheses of the naturally occurring δ-lactones (+)-tanikolide and (-)-malyngolide as well as of the unnatural (+)-enantiomer of the latter are described. Key steps in each of these syntheses were stereoselective additions of organomet
- Carda, Miguel,Rodríguez, Santiago,Castillo, Encarnación,Bellido, Alejandro,Díaz-Oltra, Santiago,Marco, J. Alberto
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p. 857 - 864
(2007/10/03)
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- D- and L-erythrose as sources of chiral quaternary carbon centers. Total synthesis of (-)-malyngolide and (+)-tanikolide
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A highly efficient and versatile approach was applied for the total synthesis of the marine natural products (-)-malyngolide and (+)-tanikolide from isopropylidene L- and D-erythrose, using a common strategy.
- Koumbis, Alexandros E.,Dieti, Kyriaki M.,Vikentiou, Myrofora G.,Gallos, John K.
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p. 2513 - 2516
(2007/10/03)
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- Enantioselective total synthesis of δ-lactonic marine natural products, (+)-tanikolide and (-)-malyngolide, via RCM reaction
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Enantioselective total synthesis of δ-lactonic marine natural products, (+)-tanikolide and (-)-malyngolide isolated from Lyngbya majuscula, was achieved by using the Sharpless asymmetric epoxidation and a ring-closing metathesis, as key reactions.
- Mizutani, Hirotake,Watanabe, Masayuki,Honda, Toshio
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p. 8929 - 8936
(2007/10/03)
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- Asymmetric hetero Diels-Alder route to quaternary carbon centers: Synthesis of (-)-malyngolide
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Conformationally constrained chiral bis(oxazoline)-metal complex catalyzed asymmetric hetero Diels-Alder reactions of Danishefsky's diene and a variety of α-keto esters constructed quaternary carbon centers enantioselectively. The reaction was utilized in
- Ghosh, Arun K,Shirai, Michio
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p. 6231 - 6233
(2007/10/03)
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- Efficient 1,8- and 1,9-asymmetric inductions in the Grignard reaction of δ- and ε-keto esters of 1,1′-binaphthalen-2-ols with an oligoether tether as the 2′-substituent: Application to the synthesis of (-)-malyngolide
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Efficient 1,8- and 1,9-asymmetric inductions in the Grignard reaction of podand-type δ- (3,4) and ε-keto esters (5,6) are achieved in the presence of MgBr2·OEt2 with up to 97 and 82% optical yields, respectively, by using 2′-[3-(2-methoxyethoxy)propoxy]-1,1′-binaphthalen-2-ol as the chiral auxiliary. The 1,8-asymmetric inductive Grignard reaction has been advantageously utilized in the key step of a synthesis of (-)-malyngolide.
- Date,Tamai,Hattori,Takayama,Kamikubo,Miyano
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p. 645 - 653
(2007/10/03)
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- Pseudo-C3-Symmetric Tertiary Alcohol Building Block via Group-Selective Hydroalumination: A Synthesis of (-)-Malyngolide
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(matrix presented) The stereocontrolled preparation of tertiary alcohol 4 and its TMS surrogate 5, which share a pseudo-C3-symmetry, is described. Compound 4 was used for the synthesis of (-)-malyngolide.
- Suzuki, Takao,Ohmori, Ken,Suzuki, Keisuke
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p. 1741 - 1744
(2007/10/03)
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- Asymmetric synthesis of quaternary centers. Total synthesis of (-)-malyngolide.
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[structure] The deracemization of 3-nonyl-3,4-epoxybut-1-ene with Pd(0) in the presence of chiral ligands using p-methoxybenzyl alcohol as a nucleophile proceeds regio- and enantioselectively to form the monoprotected vinylglycidol in 99% ee. This chiral building block was converted in seven steps to (-)-malyngolide, an antibiotic showing significant activity against Mycobacterium smegmatis and Streptococcus pyogenes. An interesting aspect involves controlling the diastereoselectivity of protonation of an enolate via a distal hydroxyl group.
- Trost,Tang,Schulte
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p. 4013 - 4015
(2007/10/03)
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- Alternative synthesis of (-)-malyngolide utilizing (-)-quinic acid
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(-)-Malyngolide, an antibiotic isolated from a blue-green algae, was synthesized starting from (-)-quinic acid.
- Matsuo, Keizo,Matsumoto, Takuya,Nishiwaki, Keiji
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p. 1213 - 1220
(2007/10/03)
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- Synthesis of (-)-malyngolide using reactions of alkylidenecarbenes
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An alkylidenecarbene has been generated by the reaction of dimethyl (diazomethyl)phosphonate (DAMP), Bu'OK and methyl ketone 6, which itself has been derived from D-mannitol in high yield. The carbene undergoes an intramolecular 1,5 C-H insertion reaction to give the chiral cyclopentane derivative 3 in good yield. It has been found that the same conversion can be conveniently carried out on a large scale with lithiotrimethylsilyldiazomethane. The double bond of 3 has been cleaved to give the keto aldehyde 2, which has been subjected to a double C1 elongation reaction via alkylidenecarbenes using DAMP and K2CO3. The resulting alkyne has been alkylated to give an intermediate 11 which has the carbon skeleton of malyngolide. Deprotection of 11, followed by elaboration of the functional groups completes the chiral synthesis of (-)-malyngolide 1.
- Ohira, Susumu,Ida, Takahiro,Moritani, Masanori,Hasegawa, Taisuke
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p. 293 - 297
(2007/10/03)
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- Stereoselective synthesis of a 2,2,5-trisubstituted tetrahydropyran chiron via 1,3- and 1,6-asymmetric induction: A total synthesis of (-)- malyngolide
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A new mode of synthesizing chiral 2,2,5-trisubstituted tetrahydropyran is described, in which two chiral centers are simultaneously introduced via facial and group selective nucleophilic acetal cleavage reaction of a bicyclic acetal 1, thereby accomplishing 1,3- and 1,6-asymmetric induction. It is revealed that acetal cleavage of the pro-R C-O bond and nucleophilic attack opposite the cleaved bond proceed preferentially. With TiCl4 and allyltrimetylsilane at -100 °C, the selectivity of acetal fission is 10:1 and that of nucleophilic attack is 12:1. This reaction is successfully applied to a total synthesis of marine antibiotics, (-)-malyngolide.
- Maezaki, Naoyoshi,Matsumori, Yuki,Shogaki, Takeshi,Soejima, Motohiro,Ohishi, Hirofumi,Tanaka, Tetsuaki,Iwata, Chuzo
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p. 13087 - 13104
(2007/10/03)
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- A new tactic for diastereo- and enantiocontrolled synthesis of (-)-malyngolide via catalytic meso-asymmetrization
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A meso-1,4-enediol bis-silyl ether 2 having bicyclo[2.2.1]heptene background has been transformed diastereo- and enantioselectively into (-)malyngolide 1, an antibiotic isolated from the blue-green marine algae, Lyngbya majuscula, via Rh(I)-(R)BINAP-catalyzed asymmetrization and diastereoselective modification of the optically active product thus obtained.
- Konno, Hiroyuki,Hiroya, Kou,Ogasawara, Kunio
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p. 6023 - 6026
(2007/10/03)
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- Synthesis of (-)-Malyngolide
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δ-Lactone (-)-malyngolide (1) was synthesized by starting from the optically active epoxide 5.Coupling of derivative 3 with propargyl anion 11 and subsequent metal-catalyzed methylation of the triple bond provided 14 incorporating all the carbon atoms of
- Floerke, Holger,Schaumann, Ernst
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p. 147 - 152
(2007/10/03)
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- New route to (-)-frontalin and (-)-malyngolide via epoxyketone rearrangement
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Synthesis of the title compounds by utilizing BF3·Et2O catalyzed ring contraction of 2,3-epoxycyclohexanones leading to 2-alkyl-2-formylcyclopentanones is described.
- Asaoka, Morio,Hayashibe, Satoshi,Sonoda, Syuzo,Takei, Hisashi
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p. 6967 - 6974
(2007/10/02)
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- Asymmetric Syntheses of (-)-Malyngolide and (-)-Frontalin by Utilizing Bakers' Yeast Reduction of S-Ethyl 2-Cyclopentanonecarboxylthioate
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Bakers' yeast reduction of S-ethyl 2-cyclopentanonecarboxylthioate affords optically pure S-ethyl (1R,2S)-2-hydroxycyclopentanecarboxylthioate which is stereoselectively converted into (-)-malyngolide and (-)-frontalin.
- Sato, Toshio,Maeno, Hajime,Noro, Tomohiro,Fujisawa, Tamotsu
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p. 1739 - 1742
(2007/10/02)
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- ASYMMETRIC SYNTHESES BASED ON HEXAHYDRO-4,4,7-TRIMETHYL-1,3-BENZOXATHIANS
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Earlier work concerned with a highly stereoselective asymmetric synthesis based on a 1,3-oxathiane as the chiral auxiliary reagent is reviewed and recent applications to the synthesis of the four stereoisomers of malyngolide, of (R)-(+)-γ-caprolactone (a
- Eliel, Ernest L.
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- A SYNTHESIS OF THE MARINE ANTIBIOTIC (-)-MALYNGOLIDE FROM D-GLUCOSE
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(-)-Malyngolide, an antibiotic from the marine blue-green alga Lyngbya majuscula, was synthesized in about 30 percent yield from methyl 4,6-O-benzylidene-2-deoxy-α-D-erythro-hexopyranosid-3-ulose, a chiral synthon easily derived from commercially availabl
- Pougny, Jean-Rene,Rollin, Patrick,Sinay, Pierre
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p. 4929 - 4932
(2007/10/02)
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- AN ASYMMETRIC TOTAL SYNTHESIS OF A NEW MARINE ANTIBIOTIC-MALYNGOLIDE
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(-)-Malyngolide was synthesized from (S)-2-hydroxy-2-nonyl-6-heptenal, prepared in high optical yield by an asymmetric synthesis using (S)-2-(anilinomethyl)pyrrolidine as a chiral auxiliary.
- Sakito, Yoji,Tanaka, Shin,Asami, Masatoshi,Mukaiyama, Teruaki
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p. 1223 - 1226
(2007/10/02)
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