Sugar-Derived Aziridines:  Functionalization via Lithiation of the Aziridine Ring

Bisseret, Philippe; Bouix‐Peter, Claire; Jacques, Olivier; Henriot, and Stéphanie; Eustache, Jacques

doi:10.1021/ol990841e

Cited by 27 publications

(15 citation statements)

References 6 publications

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“…Since there are a lot of experimental data regarding the organolithium reactions 27–34, 49–55, the present findings will surely be helpful in characterizing the possible reaction mechanisms in solutions with Li‐containing systems. More testing examples are still underway for further characterization.…”

Section: Resultsmentioning

confidence: 88%

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Test and modification of the van der Waals' radii employed in the default PCM model

Chasse

Fang

2008

Int J of Quantum Chemistry

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ABSTRACT:High level ab initio calculations at the B3LYP/6-311ϩϩG(d,p) and MP2(full)/6-311ϩϩG(d,p) levels employing PCM/UA0 model with different van der Waals' radii for the systems that contain lithium atoms have been carried out, in order to see if the van der Waal's radius for lithium atom employed in the default PCM/UA0 model is proper or not. Comparative analysis indicated that the van der Waals' radius for alkali metals, especially for lithium atom in the default PCM/UA0 model within the Gaussian 03 package, is too small, which causes erroneous redundant imaginary frequencies (RIFs) in the characterization of Li-containing compounds from moderate to big size. A new set of van der Waals' atomic radii based on QTAIM, proposed by Bader, was suggested for a better choice in the characterization of compounds containing alkali metals, for which it can effectively avoid the erroneous RIFs for corresponding geometries of these Li-containing systems.

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Section: Resultsmentioning

confidence: 88%

“…Generally, THF is frequently employed as a solvent for Li-containing system, while there are a lot of examples with other solvents, for example, CH 2 Cl 2 , toluene, cumene, etc. [27][28][29][30][31][32][33][34].…”

Section: Introductionmentioning

confidence: 99%

Test and modification of the van der Waals' radii employed in the default PCM model

Chasse

Fang

2008

Int J of Quantum Chemistry

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“…141 Recently aziridine borane complexes have been lithiated and reacted with electrophiles. 142,143 In addition, sulfinyl aziridine (2R,3R)-176 was subjected to sulfoxide-lithium exchange and quenched with range of electrophiles, mainly aldehydes and ketones (Scheme 44). 144 Oxazolinyl aziridinyl anions have increased the scope for introducing substituents directly to the aziridine ring (Scheme 44).…”

Section: Aziridinyl Anionsmentioning

confidence: 99%

Recent Synthetic Applications of Chiral Aziridines

2000

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Due to their ready availability in chiral form, and propensity to undergo regio-and stereoselective ring opening, aziridines have found widespread use in asymmetric synthesis. This review attempts to summarise the breadth of use of chiral aziridines in synthesis that has recently been reported. Particular emphasis is put on the effect of substituents on ring openings, rearrangements and use as chiral ligands and auxiliaries.

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“…The structure and absolute configuration of 7 was confirmed by an unambiguous synthesis from diacetone D-glucose. 5 Bisseret and co-workers 8 reported a new synthesis of 7 using lithiation of an aziridine ring, whereas a highly diastereoselective reductive benzyloxymethylation of protected tartarimide was the methodology chosen by Huang and co-workers 9 in order to achieve the synthesis of 7. Compound 2 has also been synthesized by Lee and Jeong 10 from commercial D-glucurono-d-lactone and by Clapés and co-workers, 11 together with 3, 5, 2,5,6-trideoxy-2,5-imino-D-altritol (6-deoxy-DALDP, 6), 7, and ent-7 (= 8), through an enzymatic reaction similar to that mentioned above.…”

mentioning

confidence: 99%

Polyhydroxylated Pyrrolidines: Synthesis of Trideoxy-2,5-iminohexitols

Izquierdo¹,

Plaza²,

Tamayo³

et al. 2008

Synthesis

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A series of naturally occurring pyrrolidine alkaloids and analogues, with the general structure of trideoxy-2,5-iminohexitols (imino-or azasugars), have been enantiosynthesized using triorthogonally protected pyrrolidines, previously prepared from commercial D-fructose, as homochiral starting materials. The inhibitory activity of some of the described compounds against glycosidases and glycosyltransferases makes them potential therapeutic agents.In 1991 Wong and co-workers 2 described, for the first time, a synthetic methodology that combined an enzymatic aldol condensation reaction, giving a key intermediate 5-azido-5-deoxyhexulose, with a highly stereocontrolled intramolecular reductive amination, which afforded a trihydroxylated pyrrolidine identified as 2,5,6-trideoxy-2,5-imino-D-glucitol (6-deoxy-DGDP, 1). Two years later, 3 Wong's group, using the same methodology, reported the synthesis of 1 as well as of three new trideoxy-2,5-iminohexitols, named as 1,2,5-trideoxy-2,5-imino-D-glucitol (1-deoxy-DGDP, 2), 1,2,5-trideoxy-2,5-imino-L-altritol (ent-4 = 5), and 1,2,5-trideoxy-2,5-imino-D-mannitol (1-deoxy-DMDP, 7) 4 (see Figure 1). Compound 7 was isolated in the same year by Molyneux and co-workers from seeds 5 of Angylocalyx pynaertii (Leguminosae) and more recently, together with compounds 3 and 4, from the bark 6 and pods 7 of this plant. The structure and absolute configuration of 7 was confirmed by an unambiguous synthesis from diacetone D-glucose. 5 Bisseret and co-workers 8 reported a new synthesis of 7 using lithiation of an aziridine ring, whereas a highly diastereoselective reductive benzyloxymethylation of protected tartarimide was the methodology chosen by Huang and co-workers 9 in order to achieve the synthesis of 7. Compound 2 has also been synthesized by Lee and Jeong 10 from commercial D-glucurono-d-lactone and by Clapés and co-workers, 11 together with 3, 5, 2,5,6-trideoxy-2,5-imino-D-altritol (6-deoxy-DALDP, 6), 7, and ent-7 (= 8), through an enzymatic reaction similar to that mentioned above. Pyrrolidines 4 and 6 were also prepared by Defoin and co-workers 12 from chiral 1,2-oxazines, while the former has recently been described by Moriarty and co-workers who employed an exo-to endo-iminocyclitol rearrangement. 13 Compound 7 was shown to be a moderate competitive inhibitor versus b-mannosidase (IC 50 380 mM), 5 as well as a potent inhibitor of bovine epididymis a-L-fucosidase (IC 50 150 mM), rat epididymis b-mannosidase (IC 50 93 mM), and bovine liver b-galactosidase (IC 50 30 mM). 6,

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Sugar-Derived Aziridines: Functionalization via Lithiation of the Aziridine Ring

Abstract: Stereoselective preparation of a new arabinose-derived aziridine and functionalization of the corresponding N-BH 3 complex are described. Regio-and stereoselective aspects are discussed.

Cited by 27 publications

References 6 publications

Test and modification of the van der Waals' radii employed in the default PCM model

Test and modification of the van der Waals' radii employed in the default PCM model

Recent Synthetic Applications of Chiral Aziridines

Polyhydroxylated Pyrrolidines: Synthesis of Trideoxy-2,5-iminohexitols

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