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Open AccessJournal ArticleDOI

Unexpected formation of complex bridged tetrazoles via intramolecular 1,3-dipolar cycloaddition of 1,2-O-cyanoalkylidene derivatives of 3-azido-3-deoxy-d-allose

Marco Worch, +1 more
- 11 Aug 2008 - 
- Vol. 343, Iss: 12, pp 2118-2129
TLDR
Of the studied molecules, 3-azido-1,2-O-cyanoethylidene-3-deoxy-allopyranose provides the most suitable scaffold for intramolecular [2+3] cycloaddition under exceptionally mild conditions.
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This article is published in Carbohydrate Research.The article was published on 2008-08-11 and is currently open access. It has received 34 citations till now. The article focuses on the topics: Cycloaddition & 1,3-Dipolar cycloaddition.

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Analysis of carbohydrates and glycoconjugates by matrix-assisted laser desorption/ionization mass spectrometry: an update for 2007-2008.

TL;DR: This review is the fifth update of the original review on the application of MALDI mass spectrometry to the analysis of carbohydrates and glycoconjugates and brings coverage of the literature to the end of 2008.
Journal ArticleDOI

Analysis of carbohydrates and glycoconjugates by matrix-assisted laser desorption/ionization mass spectrometry: an update for the period 2005-2006.

TL;DR: A comprehensive review of the application of MALDI to the analysis of carbohydrates and glycoconjugates can be found in this article, where the authors provide a comprehensive overview of the literature.
Patent

Crosslinked fibers and method of making same by extrusion

TL;DR: In this paper, the first and second precursors, each possessing a core and at least one functional group known to have click reactivity, are mixed and then extruded under heat to cross-link during fiber production.
Journal ArticleDOI

Synthesis of tetrazole-fused glycosides by a tandem fragmentation-cyclization reaction.

TL;DR: This new reaction offers additional advantages for the synthesis of tetrazolo-sugars, including the ready availability of the starting materials, experimental simplicity, mild conditions, and good yields.
Patent

Bioadhesive composition formed using click chemistry

TL;DR: In this paper, the cycloaddition reaction of a first component possessing at least one azide group with a second component possessing alkyne group was used to construct a compound for adhesives or sealants in medical and surgical applications.
References
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Purification of laboratory chemicals

TL;DR: Common physical techniques used in purification chemical methods used in Purification purification of organic chemicals Purification of inorganic and metal organic chemicals general methods for the purification classification of classes of compounds and natural products biochemicals and related products as mentioned in this paper.
Journal ArticleDOI

5-Substituted-1H-tetrazoles as carboxylic acid isosteres: medicinal chemistry and synthetic methods

TL;DR: A survey of representative literature procedures for the preparation of 5-substituted-1H-tetrazoles, focusing on preparations from aryl and alkyl nitriles, is presented in sections by generalized synthetic methods.
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Frequently Asked Questions (16)
Q1. What contributions have the authors mentioned in the paper "Unexpected formation of complex bridged tetrazoles via intramolecular 1,3-dipolar cycloaddition of 1,2-o-cyanoalkylidene derivates of 3-azido-3-deoxy-d-allose" ?

Of the studied molecules, 3-azido-1,2-O-cyanoethylidene-3-deoxy-allopyranose provides the most suitable scaffold for intramolecular [ 2+3 ] cycloaddition under exceptionally mild conditions. 

They can serve as bioisosteres of carboxylic acids,1,2 as precursors of nitrogen-containing heterocycles, and as lipophilic spacers in pharmaceuticals. 

Formation of exo-cyanoethylidene 5 is expected to be kinetically favored due to an attack from the sterically less hindered convex side of bicyclic 8. 

22–24 Myers et al. showed that cyanoethylidenecompounds of mannose, glucose, and galactose can be converted to anomeric cyanides under acid promotion without an exogenous cyanide source. 

Anomeric deprotection of 10 by treatment with hydrazinium acetate for 3 h at 50 C and subsequent acetylation with pyridine/Ac2O led to the formation of 11 as a mixture of anomers (a:b = 1:2.9) in 41% yield over 2 steps. 

Proper spatial orientation of azido and cyano groups within endo-cyanoethylidene 9 obviously leads to a fast irreversible intramolecular cycloaddition forming tetrazole 6. 

Their results highlight the capability of carbohydrates to act as scaffolds for the precise positioning of functional groups productive for a specificchemical reaction. 

A potentially useful method for the preparation of 1,5-disubstituted tetrazoles is the [2+3] cycloaddition of organic azides to nitriles. 

To isolate and characterize cyanoethylidene intermediate 5, the authors reacted 3 with TMSCN (5 equiv) and catalytic amounts of Lewis acid (0.2 equiv SnCl4) at room temperature. 

When using 60% formic acid for the cleavage of the isopropylidene protecting groups of 1, the authors observed the formation of two different formylated side products, which could subsequently be converted with NaOMe/MeOH to the completely deprotected 3-azido3-deoxy-D-allose 2 existing predominantly as b-pyra-O OHHON3 OHOAcON OOAcO N N NOO ON3 O Oa or b c OH1 267e OHON OOHO N N NScheme 1. 

Starting from 3-azido-3-deoxy-1,2:5,6-di-O-isopropylidene-a-D-allofuranose 126 the authors obtained the peracetylated allopyranose derivative 3 using two different pathways. 

Treatment with acetic anhydride in pyridine afforded peracetylated b-pyranose 3 in 91% yield over 3 steps besides small amounts of the corresponding a- and bfuranose and a-pyranose forms. 

Since the endo-cyanoethylidene derivative 21 could be isolated in the allofuranose case, the authors conclude thatHOMe OOON3 OHOMe16 a7, 78%. 

In the course of their investigations toward the Lewis-acid promoted synthesis of glycosyl cyanides, the authors now observed an unexpected side reaction leading for the first time to complex bridged tetracyclic ring systems via 1,3-dipolar cycloaddition of intermediate cyanoethylidene derivatives of 3-azidoallose even at room temperature. 

In the course of their program directed at the synthesis of sugar diamino acids (SDAs) as building blocks of oligosaccharide mimetics,25 the authors were interested in glycosyl cyanide 4 of 3-azido-3-deoxy-D-allopyranose (Scheme 1). 

Tetrazole 6 shows a 13C NMRO OAcAcON3 OAcOAc O OAc AcON3 OAcCNd354OAcON3 OOAcOCNdMeOH, 2 h; (b) 2 M HCl, 6 h; (c) Ac2O, pyr, overnight, 91% [(a) + (c)], e) NaOMe, MeOH, 14 h, 84%.mpounds 5 and 6.