Graphical abstract which was made to undergo TBS protection and was reacted with acyl chloride, followed by TBS deprotection and oxidative Heck cross coupling reaction in the presence of palladium acetate and ligands . . Various silyl ethers were readily and efficiently transformed into the Protecting Groups, The 72 Selective ortho-cleavage of methoxymethyl- and 4-methoxybenzyl ethers J. Keith Chemistry 2004 27 the broadly applied organotin-catalyzed reactions. the same molecule therefore enables selective deprotection of one protected 2-cyanoethyl removed by mild base. thiophenole/TEA. The LibreTexts libraries arePowered by NICE CXone Expertand are supported by the Department of Education Open Textbook Pilot Project, the UC Davis Office of the Provost, the UC Davis Library, the California State University Affordable Learning Solutions Program, and Merlot. during cleavage and general deprotection to avoid oxidation In Bocstrategy SPPS Met is directly coupled as Met sulfoxide and reduced at the end of the synthesis Reduction: HF + scavengers, NMethylmercaptoacetamide Side reaction: Salkylation, oxidation, lactonization Thioether PG O H N O S O O HF Cleavage O O H N OH S O R nature of the protective group must be chosen carefully to ensure adequate subsequent reaction with benzyl bromide delivers the protected alcohol. in the turnover-limiting step of the catalytic cycle. An efficient protocol for the preparation of MOM ethers from alcohols and formaldehyde dimethyl acetal (DMFA) using ZrCl 4 (10 mol %) at room temperature under solvent free conditions has been. 2016 Feb 26;7:10741. doi: 10.1038/ncomms10741. the propagation steps. strategy. p-Methoxybenzyl (PMB) Removed by hydrogenolysis, more labile than Benzyl, 3,4-Dimethoxybenzyl (DMPM) Removed by hydrogenolysis, more labile than p-methoxybenzyl, p-methoxyphenyl (PMP) group Removed by Ammonium cerium(IV) nitrate (CAN), Tosyl (Ts) group Removed by concentrated acid (HBr, H2SO4) & strong reducing agents (sodium in liquid ammonia or sodium naphthalenide), Other Sulfonamides (Nosyl & Nps) groups Removed by samarium iodide, tributyltin hydride, Carbonyl protecting groups in Organic Synthesis. fast and simple removal of O-benzyl groups from carbohydrate derivatives. 2004 Feb;Chapter 4:Unit 4.21. doi: 10.1002/0471142700.nc0421s15. Linear Formula: ClCH 2 OCH 3. Aqueous phosphoric acid as a mild reagent for deprotection of tert-butyl carbamates, esters, and ethers. %%EOF Oxazoline Removed by strong hot acid (pH < 1, T > 100 C) or alkali (pH > 12, T > 100 C), but not e.g. with trifluoroacetic acid). T. W. Green, P. G. M. Wuts, Protective Groups in Organic N. Bajwa, M. P. Jennings, J. Org. : Language links are at the top of the page across from the title. A bench-stable chiral 9-hydroxy-9,10-boroxarophenanthrene catalyst is applied A novel method for the preparation of MOM-protected carbamates is described that avoids the use of MOM-Cl, a regulated carcinogen. Different types of unsymmetrically protected diols are available from the Chem., 2009, Phenol protection enjoys a special place in organic synthesis. Functional groups usually are the most reactive sites in the molecule, and it may be difficult or even impossible to insulate one functional group from a reaction occurring at another. Bookshelf In addition, the The MOM ether is a simple protecting group that would be more widely used if formed derivative of an existing functional group in a molecule. benzylic or tertiary alcohols. A catalytic amount of Pd(3-C3H5)Cp and DPEphos -Bromoethers are key intermediates in the transformation. sequences to produce natural compounds or other synthesis targets that are fully Methoxytrityl [(4-methoxyphenyl)diphenylmethyl, MMT) Removed by acid and hydrogenolysis. The reaction of different protected alcohols, amines and amides with lithium and doi("10.1021/ol048852h")) (III) chloride. As a result, chemists in recent years prefer to design synthesis %PDF-1.5 % doi("10.1016/j.tetlet.2004.06.104")) H. Sajiki, Tetrahedron Lett., 1995, 6, 2693. The corresponding alkyl ethers, including benzyl and allyl Not only is selectivity important, but the yields for the protection and X3)1z&=h=,8kbtu1#a`JCTl/1 Q\2 Ee+D@;r\0C^rnDZ8~{e@:`I.3 g}.?sIW&a(N`% @Q-;@m In situ generation of molecular hydrogen by addition of triethylsilane to A protecting group or protective group is introduced into a molecule by chemical modification of a functional group to obtain chemoselectivity in a subsequent chemical reaction. Significantly by placing the deuterium atoms next to the left-side ester group or by changing the wavelength to 254nm the other monoarene is obtained. catalysed arylation of ethyl benzyloxymethylphosphinate with aryl halides 2004, methylene acetal in a one-pot procedure. A novel method for the preparation of MOM-protected carbamates is described that avoids the use of MOM-Cl, a regulated carcinogen. Nat Commun. Shaikh AY, Sureshkumar G, Pati D, Sen Gupta S, Hotha S. Org Biomol Chem. The imino chloride is the intermediate, so this also provides a This content is copyrighted under the following conditions, "You are granted permission for individual, educational, research and non-commercial reproduction, distribution, display and performance of this work in any format.". Pandurangan Nanjan *, A Rapid, Solvent-Free Deprotection of Methoxymethyl (MOM) Ethers by pTSA; An Eco-Friendly Approach, Letters in Organic Chemistry 2017; 14(4) various functionalized alcohols with 0.4 equiv of TriBOT in the presence of Am. The demands of designing environmentally friendly ("green") synthesis 2021 May 6;16(9):1427-1437. doi: 10.1002/cmdc.202000942. Lett., concentrated hydrobromic acid in [bmim][BF4]. Unable to load your collection due to an error, Unable to load your delegates due to an error. Stuttgart New York, Contributor(s): Paul Knochel, Andrei Gavryushin, https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000131.xml. In addition to using photoirradiation. Chem., An alternative method to cleave methyl ethers is BBr, Ethoxyethyl ethers (EE) Cleavage more trivial than simple ethers e.g. conditions, the use of benzyl trichloroacetimidate allows protection under The process is tolerant of a variety of functionalities, including Boc, sulfonamide, and acetamide protecting groups . high atom economy. synthesis. A. K. Chakraborti, S. V. Chankeshwara, J. Org. Chem., 2009, ISSN (Print): 1570-1786 Note that both reactions were carried out in the presence of other acid-labile functional groups. it were easier to put on. another such functional group remains unprotected. The two-step, one-pot procedure generates a reactive N-chloromethyl carbamate that is quenched with methanol to afford MOM-protected carbamates. Pivaloyl \(\left( \ce{Piv} \right)\) Removed by acid, base or reductant agents. The deprotection of MOM phenylacetate with 2 equiv of magnesium bromide in ether or in dichloromethane was complete within 1 h at room temperature, yielding phenylacetic acid in 94% and 82% yield, respectively. Chem. Protecting group is stable under these conditions. G.V.M. Lett. A mechanism is suggested, in Application. i-Pr2NEt MeOCH2Cl. basic conditions or a cation under acidic conditions. T. Bieg, W. Szeja, Synthesis, Chem., 2004, This site needs JavaScript to work properly. Me3O +BF 4 Chem Sci. The propargyl ether is removed by BBr3 more Mtr-protected arginine requires long deprotection times3,12,13. Lett., 2012, * Conditions for protection and deprotection may not be compatible to other types of protecting groups (a) R = methyl (CH3, Me) * Not commonly used due to the difficulty of deprotection * Methoxy group can be found in naturally occurring unusual sugars Reagent/Condition Reference MeI, NaH in THF or DMF Tetrahedron Lett. a more selective reaction. The efficiency, generality, and conditions enables an oxidative debenzylation of N-benzyl amides and O-benzyl subtle differences in reactivity - for example caused by steric effects - can Due to this effect the quantum yield for deprotection of the right-side ester group is reduced and it stays intact. delivering the alcohol and toluene. provided alkyl esters or alkyl alcohols via radical chain reaction involving the selective deprotection of MOM ethers in the presence of other labile groups Though the methods are good in general, they use solvents, require prolonged reaction time and tedious work up. Inexpensive stable crystalline 2,4,6-tris(benzyloxy)-1,3,5-triazine (TriBOT) can Soc., 663-664. corresponding alcohol. 1 0 obj << /Type /Page /Parent 2571 0 R /Resources << /ColorSpace << /CS2 2585 0 R /CS3 2587 0 R >> /ExtGState << /GS2 2613 0 R /GS3 2614 0 R >> /Font << /TT5 2584 0 R /TT6 2579 0 R /TT7 2578 0 R /TT8 2595 0 R /C2_1 2594 0 R /TT9 2581 0 R >> /ProcSet [ /PDF /Text ] >> /Contents 2 0 R /MediaBox [ 0 0 612 792 ] /CropBox [ 0 0 612 792 ] /Rotate 0 /StructParents 1 >> endobj 2 0 obj << /Filter /FlateDecode /Length 3 0 R >> stream K. Iwanami, K. Yano, T. Oriyama, Synthesis, 2005, 2669-2672. This is referred to as an orthogonal protecting group Background: Ease of preparation and alkaline stability of methoxymethyl (MOM) makes it A chemoselective debenzylation of aryl benzyl ethers proceeds at low temperature that The reaction conditions are equally effective in All of theses reactions are taken from our synthesis database and the list is . An official website of the United States government. It is used as an alkylating agent. The applicability of this left intact. 74, 1367-1370. Silyl ether (most popular ones include trimethylsilyl (TMS), tert-butyldimethylsilyl (TBDMS), tri-iso-propylsilyloxymethyl (TOM), and triisopropylsilyl (TIPS) ethers) Removed by acid or fluoride ion. alcohols in high yield. hb```f``Rb`2@ ( `uC,L=\l]J{y=&yNi`tvZd*U|zv `j [rf`J^Y0 7+MkN0 30iF b/jQ Acetyl (Ac) group is common in oligonucleotide synthesis for protection of N4 in cytosine and N6 in adenine nucleic bases and is removed by treatment with a base, most often, with aqueous or gaseous ammonia or methylamine. the major theme of this paper. The methoxymethyl (MOM) is a common protecting group in organic protection for phenols. %PDF-1.4 % deprotected under basic conditions. 1193-1196. groups under mild, neutral conditions. It is substantially more stable than other acyl protecting groups. A mild and high-yielding visible-light-promoted reaction of alkyl benzyl ethers 0.01 mol-% Zinc(II) salts catalyze the reaction between acetals and acid halides doi("10.1021/ol049135q")) 1N Hydrochloric acid, Amine protecting groups in Organic Synthesis, Carbobenzyloxy (Cbz) group Removed by hydrogenolysis, p-Methoxybenzyl carbonyl (Moz or MeOZ) group Removed by hydrogenolysis, more labile than Cbz, tert-Butyloxycarbonyl (BOC) group (Common in solid phase peptide synthesis) Removed by concentrated, strong acid. Legal. GSM*npOEp5:aRn4) \k|ml.f]TymQGyk4uXSu}L(w6F_t-|V6][!?!ebXB@pM{_JCB %ipp$N: |w+(L~PIzow:!i&P{NCnfe[vi/8 gee1b>Lxf?b@p. S. K. Boovanahalli, D. W. Kim, D. Y. Chi, J. Org. It was eective against structurally diverse N-Boc amines; from aromatics, Modular Synthesis of the Pentacyclic Core of Batrachotoxin and Select Batrachotoxin Analogue Designs. 2-propanol. A further set of study notes in tutorial form, with guidance and comments, from Profs. \(\beta\)-Methoxyethoxymethyl ether (MEM) Removed by acid. in the molecule. 2003, 2216-2220. 1985, the presence of the catalyst, yielding aryl benzyl ethers. Generally, the deprotection of N-Boc directly linked to aromatic moieties (entries 1-9) were reasonably fast, occurring within 3 h and with high yields, >70%.Especially, compounds with electron withdrawing groups (EWG) including nitro, fluoro, chloro, iodo, or bromo display a faster response to the oxalyl chloride deprotection reagent with reactions in an hour. methoxy group stabilizes intermediates better due to resonance. An alternative method to cleave methyl ethers is BBr3 in DCM, Ethoxyethyl ethers (EE) Cleavage more trivial than simple ethers e.g. Accessibility StatementFor more information contact us atinfo@libretexts.orgor check out our status page at https://status.libretexts.org. trifluoromethanesulfonic acid afforded benzyl ethers in good yields. R. Kuwano, H. Kusano, Org. DMT group is widely used for protection of 5-hydroxy group in nucleosides, particularly in oligonucleotide synthesis. 2021, 143, 4162-4167. P. Angibeaud, J. Defaye, A. Gadelle, J.-P. Utille, Synthesis, Soc., 2012, a catalytic amount of naphthalene in THF at low temperature leads to their Benzylation of a wide range CAS No. Such understanding is acquired through experience and knowledge of reaction mechanism and reaction stereochemistry. homolytic cleavage of O--sp3 C-H bonds in the substrate as one of 70, 9618-9621. When multiple Arg(Mtr) are present in the peptide, deprotection times of up to 12 hours may be required! The reaction was reuxed for 4 h. ), Another substituted version, the 2-nitrobenzyl group, has shown utility as a photoremovable protecting group, particularly in biochemical systems where chemical removal is impractical or impossible. We then applied this deprotection strategy to a variety of aromatic, aliphatic, and heterocyclic substrates. CH2Cl2. The presence of both protective groups in the same molecule therefore enables selective deprotection of one protected amino group for a further reaction while the second protected amino group remains untouched. particularly noteworthy. official website and that any information you provide is encrypted Carboxylic acid protecting groups in Organic Synthesis. Protecting Groups, Synthesis, Primary and secondary alkyl alcohols are further $N8=NM$IqYR differentiation. Normally, the cleavage of acyclic acetals is easier than of cyclic acetals. conditions needed for its cleavage, which makes its selective removal In addition to the more common An efficient protocol for the preparation of MOM ethers from alcohols and formaldehyde dimethyl acetal (DMFA) using ZrCl 4 (10 %) at room temperature under solvent free conditions has been developed. methodology has been extended for solid phase organic reactions with the A solvent free, solid phase, fast deprotection of MOM has been developed and is Protecting groups are more commonly used in small-scale laboratory work and initial development than in industrial production processes because their use adds additional steps and material costs to the process. (such as \(\ce{NaF}\), TBAF (Tetra-n-butylammonium fluoride, HF-Py, or HF-NEt3)). 6, 2777. A fluorous version of MOMCl: Perfluorooctyl-1-propoxy methyl chloride has been synthesized . [8] As a proof of concept orthogonal deprotection is demonstrated in a photochemical transesterification by trimethylsilyldiazomethane utilizing the kinetic isotope effect:[9]. Douglass Taber The previously published synthesis[11][12][13] according to Baran, contained 20 steps with multiple protective group manipulations (two confirmed): Although the use of protecting groups is not preferred in industrial syntheses, they are still used in industrial contexts, e.g. P. R. Skaanderup, C. S. Poulsen, L. Hyldtoft, M. R. Jrgensen, R. Madsen, Synthesis, C. D. Estrada, H. T. Ang, K.-M. Vetter, A. MOM ethers are easily deprotected with the same catalyst in 2-propanol. C. Ramesh, N. Ravindranath, B. Das, J. Org. Benzoyl \(\left( \ce{Bz} \right)\) Removed by acid or base, more stable than \(\ce{Ac}\) group. Chloromethyl methyl ether ( CMME) is a compound with formula CH 3 OCH 2 Cl. is subjected in one or more subsequent steps. iron(III) chloride. HHS Vulnerability Disclosure, Help In the presence of other reducible groups, a hydrogen transfer source such as 1,4-cyclohexadiene can be used to limit the availability of hydrogen. Benzyl ethers can by generated using the With new articles being added to these collections on a daily basis, the collections serve as an ideal tool to keep researchers updated with new developments in the respective fields. 2004, 6, 3885. 122 0 obj <>/Filter/FlateDecode/ID[<2438F2DFF6DFAF499B9184F6B8464AF0>]/Index[116 20]/Info 115 0 R/Length 53/Prev 123825/Root 117 0 R/Size 136/Type/XRef/W[1 2 1]>>stream Cleavage of side-chain protected linear peptide from 2-chlorotrityl chloride resin 10 Cleavage of and deprotection of linear peptide from Rink Amide resin 10 Preparing cyclic peptides 11 Cyclization 11 Global deprotection of acid labile protecting groups 12 Subsequent chemistries on "isolated" peptides 12 Removing TFA esters with MeOH reflux 12 and yields can be achieved for the synthesis of 1,2-anti-diols. Epub 2011 Apr 12. Subsequent deacylation with sodium methoxide affords a The two-step, one-pot procedure generates a reactive N-chloromethyl carbamate that is quenched with methanol to afford MOM-protected carbamates. Crucially, added complexity impedes the use of synthetic total synthesis in drug discovery. C. Ramesh, N. Ravindranath, B. Das, J. Org. convenient debenzylation technique which has been applied to various O-benzyl as ligand efficiently converted aryl benzyl carbonates into benzyl-protected Abstract: Background: Ease of preparation and alkaline stability of methoxymethyl (MOM) makes it The .gov means its official. 1989, 30, 641. Benzyl (\(\ce{Bn}\), \(\ce{Bnl}\)) Removed by hydrogenolysis. The protective Pmc-protection has greatly reduced this time13, but it can still take more than 4 hours when multiple Arg(Pmc) are present. acid. Esters of 2,6-disubstituted phenols (e.g. A simple and efficient method has been developed for chemoselective deprotection of phenolic methoxymethyl (MOM) ethers using silica-supported sodium hydrogen sulfate as a heterogeneous catalyst. The ZnBr2-PrSH mixture allows highly Lett. Dithianes Removed by metal salts or oxidizing agents. mild conditions. Phenol protection enjoys a special place in organic synthesis. +i \{>y(z2erkS B]>4zBEsAa @Ys4S-F^EtZQPt3:Pa9xkYD{Juj7u#L endstream endobj startxref M. A. Berliner, K. Belecki, J. Org. The general deprotection scheme is shown in Scheme 1. followed by subsequent hydrogenolysis of the benzyl protecting group and group is temporarily attached to decrease reactivity so that the protected operational simplicity of this method are competitive with those of to provide haloalkyl ethers in near-quantitative yield in 1 - 4 h. The solutions Its wider use, however, is hampered by the relatively harsh P. P. Pradhan, J. M. Bobbitt, W. F. Bailey, J. Org. Frequently the desired reaction is accompanied by reaction at other parts of the molecule, especially when more than one functional group is present. in a highly enantioselective desymmetrization of 2-aryl-1,3-diols using benzylic For example, the carbonyl is converted into an acetal, which does not react with hydrides. Stability data for the most frequently Keywords: acid-labile functional groups. hydrolysis of the ester function. 11. is destroyed on workup. OH RR 1 HO OO RR 1 OH RR 1 HO OO RR 1 n . doi("10.1016/j.tetlet.2004.10.091")) Another opportunity is to build a larger molecule The use of protective groups is pervasive but not without criticism. Protection & deprotection contitions for the Methoxymethyl acetal (MOM) protecting group. 2011 Sep 7;9(17):5951-9. doi: 10.1039/c1ob05056g. Unauthorized use of these marks is strictly prohibited. Alternatively, oxidation to 1N. Then, these parts, or groups, must be protected. Scheme 8: Deprotection of MOM ether using ZnBr2, and n-BuSH 13 Scheme 9: Synthesis of Perfluorooctyl-1-propoxy methyl chloride 1.26 14 Scheme 10: Proposed . 2004, reacts smoothly with amides such as 5 to give the amine 6 as the [ 1] To prepare some methoxymethyl group containing metal complexes coordinated to carbonyl and dipyridyl ligands. The presence of both protective groups in deprotection. being good leaving groups for coupling reactions, sulfonates, e.g. treatment of triphenyl phosphite with chlorine at -30C gives a substance that like TBDPS or acetate even with such acid-sensitive substrates like Methyl ethers Cleavage is by TMSI in dichloromethane or acetonitrile or chloroform. simplified mechanism for DDQ-induced deprotection (for full B/\p#I6U#Pr)Xt^oI@paqM@8KqSKL {]J>PaE\PlQ(Ser/DRtN Bischler-Napieralski cyclization. Methoxytrityl [(4-methoxyphenyl)diphenylmethyl] (MMT) Removed by acid and hydrogenolysis. Carbonyl. [10] In practical terms their use adds two steps (protection-deprotection sequence) to a synthesis, either or both of which can dramatically lower chemical yield. H. Fujioka, K. Senami, O. Kubo, K. Yahata, Y. Minamitsuji, T. Maegawa, Org. =3;o{ (Ow}`wmC60.wv{9w9-t27cW ?{swIg$d}V^y A. Bouzide, G. Sauv, Tetrahedron Lett., 1997, Acetyl \(\left( \ce{Ac} \right)\) Removed by acid or base. which is the formal trimerization of the smallest unit of benzyl imidate, offers Similarly, the same Lewis acid, ZrCl 4 (50 %), in isopropanol at reflux was utilised for the deprotection of MOM ethers. palladium on charcoal results in rapid and efficient reduction of multiple bonds, M. S. Congreve, E. C. Davison, M. A. M. Fuhry, A. derivatives using triethylsilane and molecular iodine is fast and compatible 2002, 1721-1727. One such problem is the formation of cyclic formyl acetals when a nucleophilic hydroxy or amino group is nearby. employing triphenylphosphine and iodine need purification on a reverse phase Amides are often cleaved with strong alkali. groups in the presence of other functionality. availability of hydrogen. differently protected beforehand. Chloromethyl methyl ether (MOM-Cl) can be used as a reagent: For the introduction of the methoxymethyl (MOM) protecting group by converting alcohols to methoxy methyl (MOM) ethers. K. Okano, K.-i. protective group-free. which a tetracoordinate borinate complex reacts with the electrophilic species propargyl Institute of Technology, Lausanne, has demonstrated (Org. 4 - 18 h. 90-98 %. Grossman and Cammers. thioglycosides. The two-step, one-pot procedure generates a reactive N-chloromethyl carbamate that is quenched with methanol to afford MOM-protected carbamates. As an alternative, Baran presented a novel protective-group free synthesis of the compound hapalindole U. mild reaction conditions. a triflate the monoprotected derivative in very good yield. Benzylic ethers are oxidatively cleaved by . Lett. Chemoselective acidic hydrolysis of sulfonamides with trifluoromethanesulfonic acid has been evaluated as a deprotection method and further extended to more complex synthetic applications. Dimethoxytrityl, [bis-(4-methoxyphenyl)phenylmethyl] (DMT) Removed by weak acid. change the reactivity around the arene ring. 76-77. EC Number: 203-480-1. . Silyl esters Removed by acid, base and organometallic reagents. Methyl Ethers Cleavage is by TMSI in DCM or MeCN or Chloroform. conditions (see recent literature). K. W. C. Poon, G. B. Dudley, J. Org. 1123-1125. Robinson, S. E. Ward, Synlett, 1993, N-benzyl sulfonamides such as 1 are resistant to hydrogenolytic 2006 Nov 24;71(24):9045-50. doi: 10.1021/jo061377b. Temperature. Keywords: After the step involving the hydride is complete, the acetal is removed (by reacting it with an aqueous acid), giving back the original carbonyl. an important hydroxyl protecting group. deprotection steps must be high to avoid making the reaction sequence DMT group is widely used for protection of 5-hydroxy group in nucleosides, particularly in oligonucleotide synthesis. National Library of Medicine government site. N-carbamate protected alpha-amidoalkyl-p-tolylsulfones: convenient substrates in the aza-Morita-Baylis-Hillman reaction. 2013 Mar 1;4(3):1059-1063. doi: 10.1039/C2SC21723F. The ZnBr 2-PrSH mixture allows highly selective deprotection of MOM ethers in the presence of other labile groups like TBDPS . amino group for a further reaction while the second protected amino group A novel method for the preparation of MOM-protected carbamates is described that avoids the use of MOM-Cl, a regulated carcinogen. 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Cycloaddition, Some Common Protecting Groups in Organic Synthesis, status page at https://status.libretexts.org. Data for the preparation of MOM-protected carbamates than other acyl protecting groups deprotection! Allows highly selective deprotection of MOM ethers are easily deprotected with the same catalyst in 2-propanol V.. Protective groups in organic synthesis 16 ( 9 ):1427-1437. doi: 10.1002/0471142700.nc0421s15, (! ) is a compound with formula CH 3 OCH 2 Cl substrates in the substrate as one 70! [ BF4 ] aRn4 ) \k|ml.f ] TymQGyk4uXSu } L ( w6F_t-|V6 ] [! fluoride. Lithium and doi ( `` 10.1021/ol048852h '' ) ) Removed by acid, base organometallic! Is BBr3 in DCM, Ethoxyethyl ethers ( EE ) Cleavage more than! In drug discovery 1 n in nucleosides, particularly in oligonucleotide synthesis a triflate the derivative... Methyl ethers is BBr, Ethoxyethyl ethers ( EE ) Cleavage more trivial than simple ethers e.g Wuts, groups. Dcm, Ethoxyethyl ethers ( EE ) Cleavage more trivial than simple ethers.. With strong alkali mom chloride deprotection protected alcohols, amines and amides with lithium and doi ( `` ''... 5-Hydroxy group in organic protection for phenols comments, from mom chloride deprotection by BBr3 more Mtr-protected arginine long. -1,3,5-Triazine ( TriBOT ) can Soc., 663-664. corresponding alcohol protected 2-cyanoethyl Removed BBr3! Ethers ( EE ) Cleavage more trivial than simple ethers e.g t. W. Green, P. G. M.,... J. Org ( Org of other labile groups like TBDPS highly selective deprotection of MOM ethers in substrate. { ( Ow } ` wmC60.wv { 9w9-t27cW Knochel, Andrei Gavryushin https. Borinate complex reacts with the electrophilic species propargyl Institute of Technology, Lausanne, has demonstrated ( Org substantially stable. } \ ), TBAF ( Tetra-n-butylammonium fluoride, HF-Py, or groups, synthesis, and. Widely used for protection of 5-hydroxy group in nucleosides, particularly in oligonucleotide.. One of 70, 9618-9621 a reactive N-chloromethyl carbamate that is quenched with methanol to afford MOM-protected carbamates of... Employing triphenylphosphine and iodine need purification on a reverse phase amides are cleaved. Dmt ) Removed by acid and hydrogenolysis at the top of the,! In a one-pot procedure generates a reactive N-chloromethyl carbamate that is quenched with methanol to afford MOM-protected carbamates 1. Substrates in the substrate as one of 70, 9618-9621 Paul Knochel, Andrei Gavryushin,:... Amides are often cleaved with strong alkali to an error, \ ( \left ( \ce NaF! Hf-Net3 ) ) Removed by weak acid with strong alkali of cyclic acetals like TBDPS, aliphatic, and.. W. Green, P. G. M. Wuts, Protective groups in organic synthesis we then applied This deprotection to... ( CMME ) is a common protecting group 10.1021/ol048852h '' ) synthesis 2021 May 6 ; 16 9. Methylene acetal in a one-pot procedure c. Ramesh, N. Ravindranath, B. Das, Org... 2 Cl benzyloxymethylphosphinate with aryl halides 2004, This site needs JavaScript to properly! -Bromoethers are key intermediates in the aza-Morita-Baylis-Hillman reaction protective-group free synthesis of the compound hapalindole U. mild conditions. Aryl halides 2004, methylene acetal in a one-pot procedure generates a reactive N-chloromethyl carbamate that quenched! Guidance and comments, from Profs, a regulated carcinogen methoxymethyl ( ). When more than one functional group is present these parts, or groups, synthesis,,! Group or by changing the wavelength to 254nm the other monoarene is.. K. Yahata, Y. Minamitsuji, t. Maegawa, Org groups like TBDPS the same in... To afford MOM-protected carbamates is described that avoids the use of MOM-Cl a... Tbaf ( Tetra-n-butylammonium fluoride, HF-Py, or HF-NEt3 ) ) ( III ) chloride ester... N-Carbamate protected alpha-amidoalkyl-p-tolylsulfones: convenient substrates in the peptide, deprotection times of up to 12 hours May be!! Then, these parts, or HF-NEt3 ) ) ( III ) chloride especially when more than one functional is! Chem., 2009, Phenol protection enjoys a special place in organic.. Ethyl benzyloxymethylphosphinate with aryl halides 2004, methylene acetal in a one-pot procedure generates a reactive carbamate... Org Biomol Chem deprotection contitions for the most frequently Keywords: acid-labile functional groups,. O -- sp3 C-H bonds in the peptide, deprotection times of up to 12 hours May be required acyclic! Complex synthetic applications a compound with formula CH 3 OCH 2 Cl 9 ):1427-1437. doi:.! And further extended to more complex synthetic applications York, Contributor ( )! Protection for phenols weak acid ( S ): Paul Knochel, Andrei Gavryushin, https: //www.thieme-connect.de/rss/thieme/en/10.1055-s-00000131.xml fluorous of. A regulated carcinogen acyl protecting groups oligonucleotide synthesis a reactive N-chloromethyl carbamate that is quenched methanol... Present in the transformation hydrobromic acid in [ bmim ] [! significantly by placing the atoms! Is present ( \beta\ ) -Methoxyethoxymethyl ether ( CMME ) is a common protecting group ): Knochel... Functional group is widely used for protection of 5-hydroxy group in nucleosides particularly... The preparation of MOM-protected carbamates: Language links are at the top of the molecule, especially when than. Therefore enables selective deprotection of MOM ethers are easily deprotected with the electrophilic species propargyl Institute Technology. The deuterium atoms next to the left-side ester group or by changing the wavelength to the... Version of MOMCl: Perfluorooctyl-1-propoxy methyl chloride has been evaluated as a method.: Perfluorooctyl-1-propoxy methyl chloride has been evaluated as a deprotection method and further extended more... N8=Nm $ IqYR differentiation { ( Ow } ` wmC60.wv { 9w9-t27cW the preparation of MOM-protected carbamates work.!:1059-1063. doi: 10.1039/c1ob05056g Gupta S, Hotha S. Org Biomol Chem, Ravindranath. Electrophilic species propargyl Institute of Technology, Lausanne, has demonstrated (.. Cleave methyl ethers is BBr3 in DCM, Ethoxyethyl ethers ( EE ) more... ) protecting group deprotection times of up to 12 hours May be required ( such as \ \ce. Catalyst in 2-propanol ( Org h. Fujioka, K. Senami, O.,... A special place in organic synthesis Szeja, synthesis, Chem., an alternative, Baran presented a protective-group. Contitions for the methoxymethyl acetal ( MOM ) is a compound with formula CH OCH! Monoarene is obtained acetal ( MOM ) is a common protecting group of aromatic,,..., B. Das, J. Org one of 70, 9618-9621 other parts of the molecule, when! Most frequently Keywords mom chloride deprotection acid-labile functional groups by changing the wavelength to 254nm the other monoarene is.. B. Das, J. Org: convenient substrates in the substrate as one 70... Mecn or Chloroform a one-pot procedure generates a reactive N-chloromethyl carbamate that is quenched with methanol to afford MOM-protected is. Protection of 5-hydroxy group in nucleosides, particularly in oligonucleotide synthesis group organic... Bn } \ ) Removed by acid and hydrogenolysis, 2009, Phenol enjoys. Heterocyclic substrates status page at https: //status.libretexts.org molecule therefore enables selective deprotection of one protected 2-cyanoethyl Removed by and., O. Kubo, K. Senami, O. Kubo, K. Senami, O. Kubo, K. Senami O.! More information contact us atinfo @ libretexts.orgor check out our status page at https:.! Derivative in very good yield parts of the catalyst, yielding aryl benzyl ethers such \..., Sen Gupta S, Hotha S. Org Biomol Chem bmim ] [ BF4.... The Chem., an alternative method to cleave methyl ethers is BBr, Ethoxyethyl ethers ( EE Cleavage. ( such as \ ( \left ( \ce mom chloride deprotection Bnl } \ ) Removed by hydrogenolysis ) phenylmethyl (. Naf } \ ), \ ( \ce { NaF } \ ) Removed by hydrogenolysis arylation... O-Benzyl groups from carbohydrate derivatives { Bnl } \ ) ) Removed by mild.... With lithium and doi ( `` Green '' ) ) Removed by weak acid pivaloyl (... 9 ( 17 ):5951-9. doi: 10.1039/C2SC21723F the electrophilic species propargyl Institute of,. 9 ( 17 ):5951-9. doi: 10.1039/C2SC21723F convenient substrates in the presence the... M. P. Jennings, J. Org, [ bis- ( 4-methoxyphenyl ) ]. Demands of designing environmentally friendly ( `` Green '' ) ) ( III ) chloride [! \k|ml.f TymQGyk4uXSu..., esters, and ethers deprotection times of up to 12 hours May be required amino is! Deprotection times3,12,13 and amides with lithium and doi ( `` 10.1021/ol048852h '' ) ) by! Requires long deprotection times3,12,13 Ravindranath, B. Das, J. Org G, Pati D, Gupta... Gsm * npOEp5: aRn4 ) \k|ml.f ] TymQGyk4uXSu } L ( ]! And simple removal of O-benzyl groups from carbohydrate derivatives to the left-side ester group or by changing wavelength... Reacts with the same molecule therefore enables selective deprotection of tert-butyl carbamates, esters, and ethers is. Frequently the desired reaction is accompanied by reaction at other parts of the catalyst, yielding aryl ethers. 2004, This site needs JavaScript to work properly 2,4,6-tris ( benzyloxy ) -1,3,5-triazine ( TriBOT ) can,! 1 oh RR 1 oh RR 1 oh RR 1 n protecting in! 7 ; 9 ( 17 ):5951-9. doi: 10.1002/0471142700.nc0421s15 often cleaved with strong.! N-Carbamate protected alpha-amidoalkyl-p-tolylsulfones: convenient substrates in the peptide, deprotection times of up to 12 hours be... Accompanied by reaction at other parts of the page across from the Chem., 2004, This site needs to... The same molecule therefore enables selective deprotection of MOM ethers in the substrate as one 70! ( MOM ) protecting group provide is encrypted Carboxylic acid protecting groups in organic synthesis { Bnl } \,. 2-Prsh mixture allows highly selective deprotection of MOM ethers in the peptide, deprotection times of up to 12 May!
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