Recent Advances in the Chemistry of Aminocyclitols

Delgado, Antonio

doi:10.1002/ejoc.200800238

Cited by 57 publications

(38 citation statements)

References 105 publications

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“…These hexasubstituted chiral cyclohexanes 18 and 19 could be used for the synthesis of chiral aminocyclitols and their derivatives. 28) In addition, no racemization was observed throughout the whole process in Charts 8 and 9.…”

Section: Construction Of Isotwistane and Homoisotwistane Skeletonsmentioning

confidence: 93%

Construction of Optically Active Isotwistanes and Aminocyclitols Using Chiral Cyclohexadiene as a Common Intermediate

Harada

Kino

et al. 2016

CHEMICAL & PHARMACEUTICAL BULLETIN

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We have developed a new method for synthesizing chiral isotwistane and homoisotwistane skeletons as well as aminocyclitols in a highly stereoselective manner. These results were achieved through the use of a common intermediate, which was derived from the ytterbium-catalyzed asymmetric Diels-Alder reaction of Danishefsky diene.Key words isotwistane; homoisotwistane; aminocyclitol; Diels-Alder; asymmetric catalysis; hetero-DielsAlder Many biologically active compounds possess a cyclic skeleton with center chirality in their structure. Therefore, the stereoselective synthesis of optically active carbon frameworks is in high demand for synthetic and medicinal chemists. The Diels-Alder reaction has been widely used for this purpose to construct six-membered carbocycles, and the catalytic and enantioselective variant of this reaction has been studied for decades. 1) Our group reported the first example of the catalytic and asymmetric Diels-Alder reaction of Danishefsky diene (1) 2,3) (Chart 1). Functionalized cyclohexene 3 was obtained in optically pure form, and 3 could be transformed to cyclohexenone 4 in quantitative yield. Both functionalized compounds could be potential synthetic intermediates, and we have previously demonstrated the synthetic utility of this reaction. 4-7)In the present study, silyloxy-substituted cyclohexadiene 7 derived from 4 was shown to be a key intermediate for two types of synthetically useful chiral building blocks, i.e., the tricyclo[4.3.1.0 3,7 ] decane (isotwistane 8, n=1) and tricyclo[5.3.1.0 3,8 ] undecane (homoisotwistane 8, n=2) skeletons via the intramolecular Diels-Alder reaction, and aminocyclitol 10 via the intermolecular hetero-Diels-Alder reaction with nitrosobenzene (Chart 2). Results and DiscussionConstruction of Isotwistane and Homoisotwistane Skeletons Isotwistane is an all-carbon tricyclic compound, and its structural motif is found in natural products such as pupukeananes, [8][9][10][11][12] palhinines, [13][14][15] and seychellene. [16][17][18] These types of compounds with (homo) isotwistane skeleton were attracted by their potential for perfumery, and the difference of scent derived from their chirality could be an important research target. Due to the unique structure of isotwistanes, the total syntheses of biologically active compounds with isotwistane skeletons have been studied by many research groups. [19][20][21][22][23] Most of these studies have used the intramolecular DielsAlder reaction to build the fused structure of isotwistane. Based on these previous studies, we planned the synthesis of a chiral isotwistane skeleton by two Diels-Alder reactions: our asymmetric Diels-Alder reaction and a sequential intramolecular Diels-Alder reaction.Dienophiles 2a-d with an olefin in the side chain (R) were prepared. We expected that Lewis acidic activation of the dienophile would occur site-specifically only at the acyloxazolidinone moiety, and the Diels-Alder reaction would take place at the adjacent olefin. With the application of our ytterbium catalyst, 3) the asy...

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Section: Construction Of Isotwistane and Homoisotwistane Skeletonsmentioning

confidence: 93%

Construction of Optically Active Isotwistanes and Aminocyclitols Using Chiral Cyclohexadiene as a Common Intermediate

Harada

Kino

et al. 2016

CHEMICAL & PHARMACEUTICAL BULLETIN

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“…9 Derivatives of inositols other than phosphoinositols are also important since several of them occur in nature. Amino derivatives of inositols are present in antibiotics [10][11][12][13] and a few others act as glycosidase inhibitors. [14][15][16] Illustrative examples of natural products and biologically active compounds containing cyclitol moiety as the main core are shown in Scheme 1.…”

Section: Introductionmentioning

confidence: 99%

myo-Inositol 1,3-acetals as early intermediates during the synthesis of cyclitol derivatives

Gurale

Sardessai

Shashidhar

2014

Carbohydrate Research

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“…In this context, synthetic routes to these aminocyclitol analogues are still desired. Although chemical strategies have been widely developed,1b, d to our knowledge, chemoenzymatic methods to access aminocyclitols or nitrocyclitols have been scarcely used 1d. 8 As part of our studies on the synthesis of new glycosidase inhibitors,9 we have recently developed the first one‐pot, straightforward fructose‐1,6‐bisphosphate aldolase‐mediated synthesis of aminocyclohexitols 10.…”

Section: Introductionmentioning

confidence: 99%

Fructose‐1,6‐Bisphosphate Aldolase‐Mediated Synthesis of Aminocyclitols (Analogues of Valiolamine) and their Evaluation as Glycosidase Inhibitors

et al. 2009

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A highly stereoselective method for the preparation of nitro‐ and aminocyclitols, using fructose‐1,6‐bisphosphate aldolase, which catalyzes the aldol reaction of dihydroxyacetone phosphate (DHAP) on hydroxynitrobutanals, is reported. The key part of the synthesis is based on a one‐pot /two‐enzyme process whereby three reactions take place; rabbit muscle aldolase (RAMA) catalyzed aldolization, phytase‐catalyzed phosphate hydrolysis, and intramolecular spontaneous nitroaldolization. Two families of nitrocyclitols were obtained depending on the carbon configuration in the β position to the nitro group. Reduction of the latter afforded the aminocyclitols. Evaluation of the inhibition properties of the amines towards five commercially available glycosidases has shown selectivity for β‐glucosidase and β‐galactosidase.

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Recent Advances in the Chemistry of Aminocyclitols

Cited by 57 publications

References 105 publications

Construction of Optically Active Isotwistanes and Aminocyclitols Using Chiral Cyclohexadiene as a Common Intermediate

Construction of Optically Active Isotwistanes and Aminocyclitols Using Chiral Cyclohexadiene as a Common Intermediate

myo-Inositol 1,3-acetals as early intermediates during the synthesis of cyclitol derivatives

Fructose‐1,6‐Bisphosphate Aldolase‐Mediated Synthesis of Aminocyclitols (Analogues of Valiolamine) and their Evaluation as Glycosidase Inhibitors

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