1,2-Diacetals:  A New Opportunity for Organic Synthesis

Ley, Steven V.; Baeschlin, Daniel K.; Dixon, Darren J.; Foster, Alison; Ince, Stuart J.; Priepke, Henning; Reynolds, Dominic J.

doi:10.1021/cr990101j

Cited by 175 publications

(82 citation statements)

References 119 publications

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“…[11] Rapid and simplified routes are therefore of great advantage. Recent years have seen an increasing use of 1,2-diacetals in organic synthesis, [12] and their application to the selective protection of diequatorial 1,2-diols gives them great potential in the synthesis of many inositol phosphates and analogues. The current route arises out of our recent studies [13] on the protection of inositols with the butane-2,3-diacetal (BDA) protecting group.…”

Section: Resultsmentioning

confidence: 99%

A Definitive Synthesis ofD‐myo‐Inositol 1,4,5,6‐Tetrakisphosphate and Its EnantiomerD‐myo‐Inositol 3,4,5,6‐Tetrakisphosphate from a Novel Butane‐2,3‐diacetal‐Protected Inositol

Mills¹,

Riley²,

Liu³

et al. 2003

Chemistry A European J

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New and rapid syntheses of the enantiomeric intracellular signalling molecules d-myo-inositol 1,4,5,6-tetrakisphosphate (1 a) and D-myo-inositol 3,4,5,6-tetrakisphosphate (1 b) are described. The synthetic strategy employs the novel butane-2,3-diacetal-protected (BDA-protected) myo-inositol (+/-)-3 ab, directly accessible from myo-inositol on a large scale, and an optical resolution with diastereoisomeric (R)-(-)-acetylmandelate esters. The X-ray crystal structure of (+/-)-4, an unusual side product of acid-catalysed reaction of myo-inositol with butanedione is also presented, and the absolute configurations of 1 a and 1 b are definitively assigned by conversion of key precursors into (+)-bornesitol and L-iditol hexaacetate, respectively. Biological activity of synthetic 1 b was confirmed in comparison with the natural polyphosphate.

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Section: Resultsmentioning

confidence: 99%

A Definitive Synthesis ofD‐myo‐Inositol 1,4,5,6‐Tetrakisphosphate and Its EnantiomerD‐myo‐Inositol 3,4,5,6‐Tetrakisphosphate from a Novel Butane‐2,3‐diacetal‐Protected Inositol

Mills¹,

Riley²,

Liu³

et al. 2003

Chemistry A European J

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“…IR spectra were recorded on a Nicolet 6700 spectrometer. 1 H, 13 C, and correlation NMR spectra were obtained using a Bruker Avance 400 MHz spectrometer. Chemical shifts are given in ppm referenced to the TMS signal.…”

Section: Generalmentioning

confidence: 99%

Stereoselective reactions of a thioester butanediacetal with various electrophiles

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Wojtasek

Frąckowiak-Wojtasek

2014

Tetrahedron: Asymmetry

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“…5.22) [17]. This phenomenon, which has been attributed to torsional effects or more specifically to the locking together of the C6 hydroxymethyl and the C4 hydroxyl group, is believed to make the molecule's transition to a half chair transition state conformation more difficult [32,33]. However, on the basis of directional electronic effects observed from the ring hydroxyl groups, it was suggested that the conformation of the exocyclic C6 hydroxymethyl group of hexopyranosides may be important for their reactivity.…”

Section: Stereoelectronic Effects Of Substituents: Polyhydroxylated Pmentioning

confidence: 99%

Armed-Disarmed Concept in the Synthesis of Glycosidic Bond

Miljković

2013

Electrostatic and Stereoelectronic Effects in Carbohydrate Chemistry

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-Reid et al. reported [1] that n-pentenyl glycosides undergo chemospecific cleavage 1 ! 2 ! 3, with N-bromosuccinimide under conditions that leave a wide variety of other protecting groups unaffected ( Fig. 5.1).According to the proposed mechanism ( Fig. 5.1), the addition of water to the reaction mixture will lead to hydrolysis but the addition of alcohol or another sugar having a free hydroxyl group will lead to the formation of glycoside or a disaccharide. In the course of these studies, Fraser-Reid et al. [1] observed that sugar molecules having an acyloxy group at the C2 carbon (6 in Fig. 5.2) hydrolyzed much more slowly than if they had an alkoxy group (7 in Fig. 5.2). This observation suggested that the n-pentenyl glycoside could be made more or less reactive (it could be armed or disarmed) by the type of protecting group placed on the C2 oxygen.The ability of the C2 acyloxy group to disarm the n-pentenyl glycoside was rationalized as shown in Fig. 5.3. Thus, it can be assumed that the cyclic halonium ions 8 and 9 are formed reversibly [2] and that the electron density on the glycosidic oxygen is depleted in 2-O-acyl derivatives so that nucleophilic attack of this oxygen on the halonium ion is less favored than in the 2-O-alkyl counterpart 9. The reason for this is that the electron-withdrawing group at the C2 carbon makes the C2 carbon slightly positively charged so that the formation of another positive charge at the C1 carbon is not a favorable process [there cannot exist two positive charges on two neighboring carbons (C1 and C2) (Fig. 5.3).].Consequently, the armed glycosyl donors react with electrophiles faster than the disarmed ones, and therefore in a solution containing both an armed and disarmed glycosyl donor molecules, whereby disarmed glycosyl donor molecules have one free hydroxyl group, the reaction with an electrophile will result in crosscoupling and not self-coupling, i.e., an armed glycosyl donor will react with the disarmed one, whereas a disarmed donor will not react with itself [3] as illustrated in Fig. 5.5. The promoters for the activation of n-pentenyl group [4,5] are iodonium dicollidine perchlorate (IDCP) and N-iodosuccinimide/triethylsilyl triflate (NIS/Et 3 SiOTf).M. Miljkovic, Electrostatic and Stereoelectronic Effects in Carbohydrate Chemistry,

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1,2-Diacetals: A New Opportunity for Organic Synthesis

Cited by 175 publications

References 119 publications

A Definitive Synthesis ofD‐myo‐Inositol 1,4,5,6‐Tetrakisphosphate and Its EnantiomerD‐myo‐Inositol 3,4,5,6‐Tetrakisphosphate from a Novel Butane‐2,3‐diacetal‐Protected Inositol

A Definitive Synthesis ofD‐myo‐Inositol 1,4,5,6‐Tetrakisphosphate and Its EnantiomerD‐myo‐Inositol 3,4,5,6‐Tetrakisphosphate from a Novel Butane‐2,3‐diacetal‐Protected Inositol

Stereoselective reactions of a thioester butanediacetal with various electrophiles

Armed-Disarmed Concept in the Synthesis of Glycosidic Bond

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