Asymmetric Dihydroxylation of <scp>d</scp>-Glucose Derived α,β-Unsaturated Ester:  Synthesis of Azepane and Nojirimycin Analogues

Dhavale, Dilip D.; Markad, Shankar D.; Karanjule, Narayan S.; PrakashaReddy, J.

doi:10.1021/jo049509t

Cited by 71 publications

(11 citation statements)

References 35 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[α]${{{20\hfill \atop {\rm D}\hfill}}}$ : +18.0 ( c 1.00 in H 2 O) [lit 31. [α]${{{20\hfill \atop {\rm D}\hfill}}}$ : +19.5 ( c 2.15 in H 2 O), lit: [32] [α]${{{20\hfill \atop {\rm D}\hfill}}}$ : +21.0 ( c 0.92 in H 2 O)}; 1 H NMR (400 MHz, D 2 O): δ =3.96 (m, 2 H), 3.87 (dd, J =9.7, 2.5 Hz, 1 H), 3.79 (d, J =4.1 Hz, 1 H), 3.76 (m, 1 H), 3.05 (dd, J =14.1, 1.8 Hz, 1 H), 2.95 (dt, J =9.3, 4.4, 4.4 Hz, 1 H), 2.87 (ddd, J =14.2, 1.5, 1.5 Hz, 1 H); 13 C NMR (101 MHz, D 2 O): δ =70.1, 68.6, 65.6, 60.2, 55.6, 44.3;31,32 HR‐MS‐ESI: m / z= 164.0928, calcd. for C 7 H 16 NO 4 : 164.0923 [M+H + ].…”

Section: Methodsmentioning

confidence: 99%

Sequential Biocatalytic Aldol Reactions in Multistep Asymmetric Synthesis: Pipecolic Acid, Piperidine and Pyrrolidine (Homo)Iminocyclitol Derivatives from Achiral Building Blocks

et al. 2014

View full text Add to dashboard Cite

A multistep chemoenzymatic synthesis for stereodiverse polyhydroxypipecolic acid analogues, homoiminocyclitols and polyhydroxylated piperidine and pyrrolidine derivatives combining glycine-dependent aldolases and both d-fructose-6-phosphate aldolase (FSA) or dihydroxyacetone phosphate (DHAP)-dependent aldolases is presented. The methodology allowed the preparation of known and innovative imine-derived molecules with a great structural diversity from simple achiral substrates. The strategy consisted of two key aldol addition steps: a first aldol addition of glycine to dimethoxy-A C H T U N G T R E N N U N G acetaldehyde catalyzed by l-and d-glycine aldolases and a second aldol addition of DHAP, dihydroxyacetone, hydroxyacetone or glycolaldehyde using FSA or DHAP-dependent aldolases as catalysts to a conveniently transformed aldol adduct from the first aldol addition. Catalytic reductive amination on the aldol adducts rendered the polyhydroxypipecolic acid analogues, (homo)iminocyclitols and polyhydroxylated pyrrolidine iminocyclitols. The reported strategy is thus designed to create up to five new stereogenic centers in three steps, four of them being controlled in two enzymatic reactions. Moreover, it allowed the installation of diverse functionalities in the molecules. This was possible by taking the full advantage of using aldolases in a multistep approach by virtue of their stereocomplementarity, stereoselectivity and broad substrate tolerance.The plasmids pQE-dHapA pde and pQE-dThrA axy were transformed into E. coli strain M-15 . Cells were grown 3014

show abstract

Section: Methodsmentioning

confidence: 99%

Sequential Biocatalytic Aldol Reactions in Multistep Asymmetric Synthesis: Pipecolic Acid, Piperidine and Pyrrolidine (Homo)Iminocyclitol Derivatives from Achiral Building Blocks

et al. 2014

View full text Add to dashboard Cite

show abstract

“…Different approaches have been explored in the past years to address this challenge. Some works reported the syntheses of 1-deoxynojirimycin and its isomers employing as starting materials substrates from the chiral pool such as carbohydrates [23][24][25] or amino acids [26,27]. Other strategies started instead from different open chain precursors and were based on chemoenzymatic [28,29] or asymmetric reactions such as dihydroxylation [30], aldol reaction coupled with a reductive amination [31] or aminohydroxylation [32] transformations.…”

Section: Introductionmentioning

confidence: 99%

Preparation of 1,6-di-deoxy-d-galacto and 1,6-di-deoxy-l-altro nojirimycin derivatives by aminocyclization of a 1,5-dicarbonyl derivative

Cuffaro

Landi

D’Andrea

et al. 2019

Carbohydrate Research

View full text Add to dashboard Cite

Iminosugars are known glycosidase inhibitors which are the subject of drug development efforts against several diseases. The access to structurally-related families of iminosugars is of primary importance for running structure-activity relationship studies. In this work, the double reductive amination (aminocyclization) reaction of a dicarbonyl derivative of the Larabino series, in turn obtained from lactose, is reported. Different ratios of 1,6-di-deoxy-Dgalacto and 1,6-di-deoxy-L-altro nojirimycin derivatives were obtained depending on the amine employed in this transformation which provided an insight into the effects of their structure on the outcome of the reaction. Of particular interest were the results obtained when two enantiomeric amino acids (D-Phe-OMe and L-Phe-OMe) were used, which resulted in the inversion of the reaction stereoselectivity.

show abstract

“…Azepanols and oxo-azepines are typically constructed via the ring-expansion or cyclization of appropriately derivatized sugars or furans with pre-established substitution patterns and stereochemistry. Methods of ring-expansion and cyclization have most-commonly included reductive amination [ 19 , 20 , 25 , 26 , 27 , 28 , 29 ] or epoxide ring opening with suitable amines [ 30 , 31 ], ring-closing metathesis (RCM) [ 32 , 33 , 34 ], alkene–nitrone cycloaddition [ 35 ] and tandem Staudinger aza–Wittig reactions [ 36 ]. The Spiegel synthesis of glucosepane utilized commercially available diacetone- d -glucose ($3.20/g) as a precursor to oxo-azepine vi via a key Amadori rearrangement ( Scheme 1 b) [ 24 ].…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Substituted Oxo-Azepines by Regio- and Diastereoselective Hydroxylation

2017

View full text Add to dashboard Cite

Substituted seven-membered N-heterocycles are prevalent bioactive epitopes and useful synthons for preparing enzyme inhibitors or molecular recognition systems. To fully exploit the chemical properties of this flexible N-heterocycle scaffold, efficient methods for its diverse functionalization are required. Here we utilize the late-stage oxidation of tetrahydroazepines as an approach to access densely functionalized oxo-azepines in a total of 8 steps and ~30% overall yield from commercially available starting materials. Hydroboration of tetrahydroazepines proceeded with diastereoselectivity in a substrate-dependent manner to yield regioisomeric azepanols before their oxidation to the corresponding oxo-azepines. Regioselectivity of the hydroboration step may be improved moderately by a rhodium catalyst, albeit with loss of conversion to a competing hydrogenation pathway. Overall our method allows efficient access to azepanols and oxo-azepines as versatile epitopes and synthons with a high degree of diastereoselectivity and moderate regioselectivity.

show abstract

Asymmetric Dihydroxylation of d-Glucose Derived α,β-Unsaturated Ester: Synthesis of Azepane and Nojirimycin Analogues

Cited by 71 publications

References 35 publications

Sequential Biocatalytic Aldol Reactions in Multistep Asymmetric Synthesis: Pipecolic Acid, Piperidine and Pyrrolidine (Homo)Iminocyclitol Derivatives from Achiral Building Blocks

Sequential Biocatalytic Aldol Reactions in Multistep Asymmetric Synthesis: Pipecolic Acid, Piperidine and Pyrrolidine (Homo)Iminocyclitol Derivatives from Achiral Building Blocks

Preparation of 1,6-di-deoxy-d-galacto and 1,6-di-deoxy-l-altro nojirimycin derivatives by aminocyclization of a 1,5-dicarbonyl derivative

Synthesis of Substituted Oxo-Azepines by Regio- and Diastereoselective Hydroxylation

Contact Info

Product

Resources

About