Microwave-induced, InCl3-catalyzed Ferrier rearrangement of acetylglycals: synthesis of 2,3-unsaturated C-glycosides

Das, Saibal Kumar; Reddy, K. Anantha; Abbineni, Chandrasekhar; Roy, Jibendu Sekhar; Rao, K. Venkat; Sachwani, Rachna H.; Iqbal, Javed

doi:10.1016/s0040-4039(03)01012-8

Cited by 40 publications

(13 citation statements)

References 20 publications

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“…The use of LiBF 4 ,167 InBr 3 ,155 iodine,151 InCl 3 under microwave irradiation conditions,168,169 In(OTf) 3 ,170 Bi(OTf) 3 ,171 ZrCl 4 ,61,156 HClO 4 /SiO 2 ,172 Er(OTf) 3 ,173 MoCl 5 ,174 Yb(OTf) 3 in ionic liquids,175 PMA supported on silica gel,106 La(NO 3 ) 3 · 6 H 2 O,84 AuCl 3 ,72b and more recently of H‐USY zeolite CBV‐720,119 have all led to good yields of allyl C ‐glycosyl derivatives 185 , with excellent α‐selectivity observed in most cases (Table 30, Entries i–xiii). Similarly, good yields were also observed for related transformations of tri‐ O ‐acetyl‐ D ‐galactal ( 4 ).…”

Section: Other Nucleophiles In the Frmentioning

confidence: 99%

Recent Developments in the Ferrier Rearrangement

et al. 2013

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Glycals (1,2‐unsaturated, cyclic carbohydrate derivatives) readily undergo (catalyzed) substitution reactions at C‐1 accompanied by allylic rearrangement. This reaction, currently named Ferrier rearrangement, or the Ferrier I reaction, has established itself as a useful synthetic tool for carbohydrate transformations. By means of this reaction, glycals can be converted into highly useful 2,3‐unsaturated glycosides. This review summarizes recent developments in the use of promoters for the Ferrier rearrangement of O‐, N‐, C‐ and S‐nucleophiles with glycals.

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Section: Other Nucleophiles In the Frmentioning

confidence: 99%

Recent Developments in the Ferrier Rearrangement

et al. 2013

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“…The microwave accelerated indium catalyzed Ferrier rearrangement 8 of tri-O-acetyl-D-galactal (8) in the presence of triethylsilane consistently provided good yields (85%) of olefin 9 9 on scales ranging from 100 mg to 20 g. Deacetylation of 9 was accomplished using NaOMe in MeOH to afford diol 7, which was selectively protected at the primary alcohol as the TBS silyl ether 10. Sequential treatment of allylic alcohol 10 with trichloroacetylisocyanate and K 2 CO 3 /MeOH afforded multi-gram quantities of carbamate 11, the substrate for the key tethered aminohydroxylation reaction, in 96% yield after purification.…”

mentioning

confidence: 99%

Synthesis of the dysiherbaine tetrahydropyran core employing a tethered aminohydroxylation reaction

Cohen¹,

Chamberlin²

2007

Tetrahedron Letters

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A stereocontrolled and scalable synthesis of an advanced intermediate of the dysiherbaine tetrahydropyran core has been achieved in 11 steps and 27% overall yield. The key feature of this synthetic approach is the application of the Donohoe tethered aminohydroxylation reaction to install the amino diol and establish the four contiguous syn stereocenters on the tetrahydropyran ring.Since its isolation in 1997, (-)-dysiherbaine (1) has attracted attention in the chemical and biological communities due to its interesting structure and unique biological activity. 1 The molecular architecture of dysiherbaine (DH), characterized by a cis fused hexahydrofuro [3,2-b]pyran ring system displaying a glutamic acid appendage, has generated a great deal of interest as a synthetic target. 2,3 Our own synthetic efforts were motivated by dysiherbaine's impressive biological profile. 4 Radioligand binding assays of DH activity at ionotropic glutamate receptors indicate that DH is a potent agonist of kainate receptors. Furthermore, DH induces epilepsy-like seizures in mice and has been shown to be the most potent epileptogenic excitatory amino acid yet identified.Both the kainate receptor selectivity and potency of DH make it a valuable pharmacological tool for investigating the physiological roles of the various glutamate receptors in the CNS. 4e Assays of dysiherbaine activity at ionotropic glutamate receptors have demonstrated that DH is a potent agonist of non-NMDA type glutamate receptors, with a particularly high affinity for the KA receptor: IC 50 = 33 and 230 nM for KA and AMPA, respectively. 1 When injected into mice, DH exhibited the most potent epileptogenic activity and neurotoxic symptoms among the known excitatory amino acids. 4a Both the receptor selectivity and potency of DH make it an excellent probe to elucidate the roles of KA receptor subtypes in the CNS. Furthermore, as a neurotoxin and potent convulsant, DH may also provide insight as to targets for therapeutic intervention in the treatment of seizures. The low natural abundance of DH, however, has limited its availability, thereby impeding further studies on its mode of action. As a consequence, total synthesis of DH is required for further physiological studies.Since the initial elucidation of the dysiherbaine structure, several research groups, including our own, have independently accomplished the total synthesis of DH. The synthesis of DH previously developed in our laboratory featured a Fleet-inspired ring contraction of the δ-* Corresponding author. Tel.: 1-949-824-7089; fax: 1-949-824-7089; e-mail: archambe@uci.edu.. Supplementary Material Complete experimental procedures, product characterization, and spectral data. Supplementary data associated with this article can be found, in the online version, at Publisher's Disclaimer: This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetti...

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“…O uso de catalisadores, tais como, LiBF4, 122 InBr3, 123 iodo, 124 InCl3 em condições de irradiação de micro-ondas, 125,126 In(OTf)3, 127 Bi(OTf)3, 128 ZrCl4, 129 HClO4 / SiO2, 130 Er(OTf)3, 131 MoCl5, 132 Yb(OTf)3 em líquidos iônicos, 133 PMA suportados em sílica gel, 25 La(NO3)3•6H2O, 135 AuCl3, e zeólita H-USY CBV-720, 136 conduziu a bons rendimentos de derivados alil C-glicosil 66 e excelente seletividade em relação ao α na maioria dos casos (Esquema 7).…”

Section: Esquema 6 Formação Dos α E β-Anômeros No Rearranjo De C-ferunclassified

Recent Advances in C-Glycoside Chemistry: Application, Synthesis and Reactions

et al. 2018

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The synthesis of C-glycosides, sugar analogs in which glycosidic oxygen is substituted by a carbon atom, is of particular interest due to their usefulness as key intermediates for assembling biologically active molecules and natural products. Despite their challenging chemistry, due to their versatility, C-glycosides play a pivotal role in the development of the chemistry of novel materials and bioactive molecules. In this review, we present of various synthetic methodologies, mechanistic proposal and application for 2,3-unsaturated C-glycosides in the last twenty years.

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Microwave-induced, InCl3-catalyzed Ferrier rearrangement of acetylglycals: synthesis of 2,3-unsaturated C-glycosides

Cited by 40 publications

References 20 publications

Recent Developments in the Ferrier Rearrangement

Recent Developments in the Ferrier Rearrangement

Synthesis of the dysiherbaine tetrahydropyran core employing a tethered aminohydroxylation reaction

Recent Advances in C-Glycoside Chemistry: Application, Synthesis and Reactions

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