Help with benzylidene protective group mechanism. It is revealed that the stereoselectivity in glycosylations of benzylidene protected glucose donors are very susceptible to acceptor nucleophilicity whereas condensations of benzylidene mannose and mannuronic acid donors represent more robust glycosylation systems in terms of diastereoselectivity. I was assigned a project where I would help a few PhD candidates by protecting a few of the hydroxyl groups on D-glucose. Carbohydrate acceptors are examined and the reactivity-selectivity profile of these nucleophiles mirrored those of the model acceptors studied. The use of benzylidene acetals as protecting groups in carbohydrate chemistry is utterly important. The change in stereoselectivity with decreasing acceptor nucleophilicity is related to a change in reaction mechanism shifting from the SN2 side to the SN1 side of the reactivity spectrum. Introduction Trichinella spiralis is a parasitic nematode that can establish itself in the intestinal epithelia of carnivorous animals.
S. Van der Vorm, T. Hansen, H. S. Overkleeft, G. A. Together they form a unique fingerprint. Copyright © 2011 Elsevier Ltd. All rights reserved. Acetal formation is generally thought to go through oxocarbenium ions and addition to those rather than an SN2 mechanism, New comments cannot be posted and votes cannot be cast. author = "{Van der Vorm}, S. and T. Hansen and Overkleeft, {H. S.} and {Van der Marel}, {G. endobj The reaction: http://i.imgur.com/Zgtj6fZ.png. The other methoxy group then leaves in the same way, forming an oxocarbenium which the other alcohol adds into. AB - A set of model nucleophiles of gradually changing nucleophilicity is used to probe the glycosylation reaction mechanism. We use cookies to help provide and enhance our service and tailor content and ads. By continuing you agree to the use of cookies, Vrije Universiteit Amsterdam data protection policy. Van der Marel, J. D.C. Codée*, Research output: Contribution to Journal › Article › Academic › peer-review. The most important protecting groups in carbohydrate chemistry are reviewed. 21 0 obj endobj Results and discussion. So I'm doing a project in my Advanced Organic lab course. In recent years, the mechanism has been investigated for borane mediated openings and it seems likely that the regioselectivity is determined by borane, rather than Lewis acid. <>/Subtype/Link/Rect[121.09 184 138.35 193]>> 12 The structure of oxidation product 8 was confirmed unambiguously by single‐crystal X‐ray analysis (Figure 1 ). Press question mark to learn the rest of the keyboard shortcuts. Thing is, now I'm writing a report on the experiment, and I can't seem to find the mechanism for the 4-OH,6-OH protection reaction with Benzaldehyde dimethyl acetal. <>/Subtype/Link/Rect[476.34 545 527 553]>> Also please don't use this sub to cheat on your exams!! Under acidic conditions, the dimethyl acetal can kick out methanol to form the oxocarbenium ion, which one of the alcohols of glucose then attacks. CopyCopied, XTVRQMKOKFFGDZ-ZLUZDFLPSA-N
Glycosylations of ethanol-based acceptors, bearing varying amounts of fluorine atoms, report on the dependency of the stereochemistry in condensation reactions on the nucleophilicity of the acceptor. The set of model ethanol acceptors thus provides a simple and effective “toolbox” to investigate glycosylation reaction mechanisms and report on the robustness of glycosylation protocols.". Predicted data is generated using the US Environmental Protection Agency’s EPISuite™. Three different glycosylation systems were scrutinized, that differ in the reaction mechanism, that-putatively-prevails during the coupling reaction. The set of model ethanol acceptors thus provides a simple and effective “toolbox” to investigate glycosylation reaction mechanisms and report on the robustness of glycosylation protocols. 26 0 obj Either pointing me to litterature that shows the mechanism, or got an idea of how to write it? This should follow a simple mechanism similar to a typical acid-catalyzed ether synthesis (like this one). Benzylidene acetals are used as protecting groups in glycochemistry. The set of model ethanol acceptors thus provides a simple and effective “toolbox” to investigate glycosylation reaction mechanisms and report on the robustness of glycosylation protocols. Copyright © 2020 Elsevier B.V. or its licensors or contributors. The allylation one is fine, but the second one really bugs me. UR - http://www.scopus.com/inward/record.url?scp=85014125732&partnerID=8YFLogxK, UR - http://www.scopus.com/inward/citedby.url?scp=85014125732&partnerID=8YFLogxK. The change in stereoselectivity with decreasing acceptor nucleophilicity is related to a change in reaction mechanism shifting from the SN2 side to the SN1 side of the reactivity spectrum. benzylidene 1-O-alkyl protected glucose [11] or used enzymes to achieve selectivity [12]. Press J to jump to the feed. Post your questions about chemistry, whether they're school related or just out of general interest. So far, so well, everything on the lab went smooth. endobj The change in stereoselectivity with decreasing acceptor nucleophilicity is related to a change in reaction mechanism shifting from the SN2 side to the SN1 side of the reactivity spectrum. It is revealed that the stereoselectivity in glycosylations of benzylidene protected glucose donors are very susceptible to acceptor nucleophilicity whereas condensations of benzylidene mannose and mannuronic acid donors represent more robust glycosylation systems in terms of diastereoselectivity. <>/Subtype/Link/Rect[279.34 210 289.98 219]>> 27 0 obj endobj CopyCopied, Validated by Experts, Validated by Users, Non-Validated, Removed by Users, Predicted data is generated using the ACD/Labs Percepta Platform - PhysChem Module, Predicted data is generated using the US Environmental Protection Agency’s EPISuite, Click to predict properties on the Chemicalize site, For medical information relating to Covid-19, please consult the, ACD/Labs Percepta Platform - PhysChem Module, US Environmental Protection Agency’s EPISuite, Compounds with the same molecular formula, Search Google for structures with same skeleton. and Cod{\'e}e, {J. D.C.}". A.} It is revealed that the stereoselectivity in glycosylations of benzylidene protected glucose donors are very susceptible to acceptor nucleophilicity whereas condensations of benzylidene mannose and mannuronic acid donors represent more robust glycosylation systems in terms of diastereoselectivity. The reaction conditions are equally effective in … 13 1 ORTEP diagram of compound 8 . <>/Subtype/Link/Rect[132.25 197 142.76 206]>> Acetals and ketals are of fundamental importance in carbohydrate chemistry and their chemistry is presented first. Present address: Department of Chemistry, McGill University, Montréal, Québec, Canada H3A 2K6. Glycosylations of ethanol-based acceptors, bearing varying amounts of fluorine atoms, report on the dependency of the stereochemistry in condensation reactions on the nucleophilicity of the acceptor. 25 0 obj The 4,6-benzylidene acetal can be opened selectively, by a number of … The required dideoxyhexose donor was synthesized in a series of high-yielding steps from glucose utilizing the p-methoxyphenyl glycoside. By continuing you agree to the use of cookies. N2 - A set of model nucleophiles of gradually changing nucleophilicity is used to probe the glycosylation reaction mechanism. endobj title = "The influence of acceptor nucleophilicity on the glycosylation reaction mechanism". It is revealed that the stereoselectivity in glycosylations of benzylidene protected glucose donors are very susceptible to acceptor nucleophilicity whereas condensations of benzylidene mannose and mannuronic acid donors represent more robust glycosylation systems in terms of diastereoselectivity. Log Octanol-Water Partition Coef (SRC): Log Kow (KOWWIN v1.67 estimate) = -0.22 Boiling Pt, Melting Pt, Vapor Pressure Estimations (MPBPWIN v1.42): Boiling Pt (deg C): 430.17 (Adapted Stein & Brown method) Melting Pt (deg C): 162.14 (Mean or Weighted MP) VP(mm Hg,25 deg C): 1.4E-010 (Modified Grain … <>/Subtype/Link/Rect[456.1 275 471.34 284]>> I've been using some time to try to find out one for myself aswell. %PDF-1.4 If borane is not activated, Lewis acid is the most electrophilic species that thus adds to O-6 and hence generates the 4-O-benzyl ether. These compounds can also be oxidized to carboxylic acids in order to open important biological molecules, such as glycosaminoglycans, to other routes of synthesis. c1ccc(cc1)C2OC[C@H]([C@@H](O2)[C@@H]([C@H](C=O)O)O)O
1.06.4.3.3 Regioselective hydrogenolysis of dioxane- and dioxolane-type benzylidene acetals 235 1.06.4.3.4 Hydrogenolysis of molecules carrying dioxane and dioxolane rings 236 1.06.4.3.5 Hydrogenolysis of symmetrical ketals 237 1.06.4.3.6 Oxidative cleavage of dioxane- and dioxolane-type benzylidene acetals 241 1.06.5 Protection of Amine 242 <>/Subtype/Link/Rect[59.5 93 74.56 102]>> Please do not post entire problem sets or questions that you haven't attempted to answer yourself. endobj While preparing the partially protected glucose 1 from α-allyl-4,6-benzylidene glucoside 2 (Scheme (Scheme1), 1), we observed that mono-benzylation could be achieved, if instead of DMF and the usual reagents' combination (i.e. I guess it's somehow basic acid-catalysed substitution with CH3OH as a leaving group, but I can't seem to make it fit. <>stream 29 0 obj ScienceDirect ® is a registered trademark of Elsevier B.V. ScienceDirect ® is a registered trademark of Elsevier B.V. Regioselective reductive openings of 4,6-benzylidene acetals: synthetic and mechanistic aspects, Dedicated to Professor András Lipták on the occasion of his 75th birthday. Dive into the research topics of 'The influence of acceptor nucleophilicity on the glycosylation reaction mechanism'. When borane is activated by Lewis acids, borane is the most electrophilic species that consequently coordinates to the most nucleophilic oxygen of the acetals, usually O-6. <>/Subtype/Link/Rect[125.14 466.5 193.31 473.5]>> Powered by Pure, Scopus & Elsevier Fingerprint Engine™ © 2020 Elsevier B.V. We use cookies to help provide and enhance our service and tailor content. The change in stereoselectivity with decreasing acceptor nucleophilicity is related to a change in reaction mechanism shifting from the SN2 side to the SN1 side of the reactivity spectrum. abstract = "A set of model nucleophiles of gradually changing nucleophilicity is used to probe the glycosylation reaction mechanism. Results and discussion While preparing the partially protected glucose 1 from α-allyl-4,6-benzylidene glucoside 2 (Scheme 1), we observed that mono-benzylation could be achieved, if instead of DMF and the 32 0 obj <>/Subtype/Link/Rect[125.37 476.5 230.06 483.5]>> Benzylidene acetals and dimethyl acetals have thermodynamic tendency to form six- and five-membered rings, respectively. 24 0 obj The set of model ethanol acceptors thus provides a simple and effective “toolbox” to investigate glycosylation reaction mechanisms and report on the robustness of glycosylation protocols. The influence of acceptor nucleophilicity on the glycosylation reaction mechanism. Three different glycosylation systems were scrutinized, that differ in the reaction mechanism, that-putatively-prevails during the coupling reaction. Benzylidene is an archaic term for compounds of the type PhCHX 2 and PhCH= substituents (Ph = C 6 H 5). A regioselective reductive ring opening of benzylidene acetals in carbohydrate derivatives using triethylsilane and molecular iodine is fast and compatible with most of the functional groups encountered in oligosaccharide synthesis, and offers excellent yields.