- Stereoselective allylation reactions of acyclic and chiral α-amino-β-hydroxy aldehydes 3: Total synthesis of (+)-1-epi-castanospermine
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Stereoselective allylation reactions of acyclic, chiral α-amino-β-hydroxy aldehydes containing four contiguous stereocenters were conducted. Allylation mediated by MgBr2?OEt2 afforded the anti-product. A plausible mechanism of the allylation reaction is also described. The resulting allylation product was used for the total synthesis of (+)-1-epi-castanospermine.
- Myeong, In-Soo,Ham, Won-Hun
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p. 3832 - 3839
(2019/06/17)
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- Concise synthesis of 1-epi-castanospermine
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1-epi-Castanospermine (5) was synthesized from readily available 2,3,4,6-tetra-O-benzyl-1-deoxynojirimycin (11) in 9 steps and 21% overall yield, with selective debenzylation, Barbier reaction and reductive amination as the main reaction steps.
- Cheng, Bin,Li, Yi-Xian,Jia, Yue-Mei,Yu, Chu-Yi
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p. 1688 - 1692
(2017/07/27)
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- Synthesis of C1- and C8a-epimers of (+)-castanospermine from d-glucose derived γ,δ-epoxyazide: Intramolecular 5-endo epoxide opening approach
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A concise synthesis of two diastereomers of (+)-castanospermine namely 1- and 8a-epi-castanospermine 1b and 1c, respectively, is reported from d-glucose. The methodology involves stereoselective cross metathesis of d-glucose derived alkene 2 with 4-bromo-
- Kalamkar, Navnath B.,Puranik, Vedavati G.,Dhavale, Dilip D.
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p. 2773 - 2778
(2011/04/27)
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- Synthesis of polyhydroxylated pyrrolizidine and indolizidine compounds and their glycosidase inhibitory activities
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The synthesis of the natural product 3-epi-casuarine and two tricyclic ether bridged analogues, plus 7-deoxy-3,6-diepi-casuarine, 7-epi-australine, 1-epi-castanospermine and 1,6-diepi-castanospermine is described. The glycosidase inhibitory activities of
- Ritthiwigrom, Thunwadee,Nash, Robert J.,Pyne, Stephen G.
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experimental part
p. 9340 - 9347
(2011/02/23)
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- A flexible approach to azasugars: asymmetric total syntheses of (+)-castanospermine, (+)-7-deoxy-6-epi-castanospermine, and (+)-1-epi- castanospermine
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The asymmetric total synthesis of natural azasugars (+)-castanospermine, (+)-7-deoxy-6-epI-castanospermine, and synthetic (+)-1-epi-castanospermine has been accomplished in nine to ten steps from a common chiral building block (S)-8. The method features a powerful chiral relay strategy consisting of a highly diastereoselective vinylogous Mukaiyama-type reaction with either chiral or achiral aldehydes (≥ 95% de; de = diastereomeric excess) and a diastereodivergent reduction of tetramic acids, which allows formation of three continuous stereogenic centers with high diastereo-selectivities. The method also provides a flexible access to structural arrays of 5-(α-hydroxyalkyl) tetramic acids, such as 17/34, and 5-(α-hydroxyalkyl)-4-hydroxyl-2- pyrrolidinones, such as 18 and 25/35 a. The method constitutes the first realization of the challenging chiral synthons A and D and thus of the conceptually attractive retrosynthetic analysis shown in Scheme 1 in a highly enantioselective manner.
- Liu, Gang,Wu, Tian-Jun,Ruan, Yuan-Ping,Huang, Pei-Qiang
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experimental part
p. 5755 - 5768
(2010/08/19)
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- Synthesis of (+)-1-epi-castanospermine from l-sorbose
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Diastereoselective synthesis of 1-epi-castanospermine (2) from l-sorbose is described. The successful approach involved the use of 8-azido-2,8-dideoxy-α-l-gulo-oct-4-ulo-4,7-furanosononitrile intermediate (17). This compound was easily made in five steps
- Izquierdo, Isidoro,Tamayo, Juan A.,Rodríguez, Miguel,Franco, Francisco,Lo Re, Daniele
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p. 7910 - 7913
(2008/12/21)
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- A concise approach to (+)-1-epi-castanospermine
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A concise enantioselective synthesis of (+)-1-epi-castanospermine (2) is described, which featured the use of chiral non-racemic tetramic acid derivative 5 as a synthetic equivalent of the challenging synthon A through a highly diastereoselective vinylogo
- Wu, Tian-Jun,Huang, Pei-Qiang
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p. 383 - 386
(2008/09/17)
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- Intramolecular 5-endo-trig aminomercuration of β-hydroxy-γ- alkenylamines: Efficient route to a pyrrolidine ring and its application for the synthesis of (+)-castanospermine and analogues
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The intramolecular aminomercuration reaction of sugar-derived β-hydroxy-γ-alkenylamines 8a-c undergoes 5-endo-trig cyclization in high yield. The sugar-substituted pyrrolidines thus obtained were elaborated to the synthesis of polyhydroxylated indolizidin
- Karanjule, Narayan S.,Markad, Shankar D.,Shinde, Vaishali S.,Dhavale, Dilip D.
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p. 4667 - 4670
(2007/10/03)
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- Novel synthesis of castanospermine and 1-epicastanospermine
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(Chemical Equation Presented) Polyhydroxylated indolizidines have potential for treatment of HIV, hepatitis C and HSV infection, multiple sclerosis, angiogenesis, cancer, and diabetes. A new synthetic approach to the title compounds from a 5-C-methoxypyra
- Cronin, Linda,Murphy, Paul V.
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p. 2691 - 2693
(2007/10/03)
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- Synthesis of (-)-7-Epiaustraline and (-)-1-Epicastanospermine
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Highly efficient and selective syntheses of the title compounds are described. The cornerstone of the synthetic plan is the tandem inter [4 + 2]/inter [3 + 2] cycloaddition process. These syntheses differ from previous applications of this strategy in that they incorporate an alkylation in the hydrogenolysis step to close the second ring of the azabicyclic systems. Notable features of the sequence are (1) the highly regio- and stereoselective [3 + 2] cycloaddition of nitronate 15 with siloxymethyl (Z)-β-silylvinyl ketone (Z)-22b and (2) the highly selective reduction of the resulting ketone 24a with L-Selectride. A single-crystal X-ray structure analysis of synthetic (-)-7-epiaustraline confirmed that the targeted structure was successfully synthesized. This stimulated a reexamination of the structural assignment of the natural product. (-)-1-Epicastanospermine was synthesized in four steps from the common intermediate 27a. The absolute configuration of (-)-1-epicastanospermine was assured by single-crystal X-ray structure analysis of intermediate (-)-27a. Thus, the sign of the optical rotation had to be revised. The overall efficiency of these syntheses were 9 steps and 23% yield for (-)-7-epiaustraline and 10 steps and 20% yield for (-)-1-epicastanospermine.
- Denmark, Scott E.,Herbert
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p. 2887 - 2896
(2007/10/03)
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- Synthesis of (+)-Castanospermine and 1-Epicastanospermine from D-Glucofuranurono-6,3-lactone by Reformatsky Reaction
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Starting from 5-O-(tert-butyldimethylsilyl)-1,2-O-isopropylidene-α-D-gluco- (2a) or -β-L-idofuranurono-6,3-lactone (2b), 7-deoxyoctofuranose derivatives 5a, 5b, 7a and 7b have been synthesized by chain extension at C-6 by Reformatsky reaction followed by
- Grassberger, Vera,Berger, Andreas,Dax, Karl,Fechter, Martin,Gradnig, Guenther,Stuetz, Arnold E.
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p. 379 - 390
(2007/10/02)
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- Total Syntheses of (+)-Castanospermine and (+)-1-Epicastanospermine and Their 1-O-Acyl Derivatives from a Common Chiral Building Block
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Stereoselective total syntheses of (+)-castanospermine (1) and (+)-1-epicastanospermine (2) and their 1-O-acyl derivatives 3 - 5 have been achieved via a noncarbohydrate-based approach utilizing allylic alcohol as a common chiral building block.Epoxide 10
- Ina, Hiroji,Kibayashi, Chihiro
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- An efficient, highly stereoselective synthesis of (+)-castanospermine
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An efficient, highly stereoselective synthesis of (+)-castanospermine (1) has been achieved from 1,2-0-isopropylidene-α-Dglucofuranurono-6,3-lactone (2).
- Anzeveno, Peter B.,Angell, Paul T.,Creemer, Laura J.,Whalon, Michael R.
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p. 4321 - 4324
(2007/10/02)
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- A HIGHLY STEREOSELECTIVE TOTAL SYNTHESIS OF (+/-)CASTANOSPERMINE
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An efficient synthesis of (+/-)castanospermine based on the bromine addition to 7-oxabicyclohept-5-en-2-one benzyl acetal is presented.
- Reymond, Jean-Louis,Vogel, Pierre
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p. 705 - 706
(2007/10/02)
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- Chelate Selectivity in Chelation-Controlled Allylations. A New Synthesis of Castanospermine and Other Bioactive Indolizidine Alkaloids
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An efficient synthesis of polyhydroxylated indolizidine alkaloids relies on new heteroatom-selective Sakurai reactions with TiCl4.
- Hamana, Hiroshi,Ikota, Nobuo,Ganem, Bruce
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p. 5492 - 5494
(2007/10/02)
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- TOTAL SYNTHESIS OF (+)-CASTANOSPERMINE FROM D-MANNOSE
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A total synthesis of (+)-castanospermine (2) has been achieved starting from D-mannose by a route adopting a double-cyclization process (5c-6) as the key step.
- Setoi, Hiroyuki,Takeno, Hidekazu,Hashimoto, Masashi
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p. 4617 - 4620
(2007/10/02)
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- TOTAL SYNTHESES OF (+)-CASTANOSPERMINE AND (+)-DEOXYNOJIRIMYCIN
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The absolute configuration of castanospermine has been determined by total synthesis to be as shown in 1.
- Bernotas, Ronald C.,Ganem, Bruce
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p. 165 - 168
(2007/10/02)
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