Efficient, Optimized Applications ofp-Nitrophenyl Active Ester Temporarily Protecting Groups Together with Simultaneous Activation in Synthesis of Special Glu and Lys Peptides

1997 ◽  
Vol 44 (5) ◽  
pp. 519-526 ◽  
Author(s):  
Gy. Szókán ◽  
M. Almás ◽  
A. Kótai ◽  
A. R. Khlafulla
Keyword(s):  
Protecting Groups ◽  
Active Ester ◽  
Simultaneous Activation

Synthesis of cyclic peptide disulfide–PHPMA conjugates via sequential active ester aminolysis and CuAAC coupling

2016 ◽  
Vol 7 (4) ◽  
pp. 970-978 ◽  
Author(s):  
Kemal Arda Günay ◽  
Harm-Anton Klok
Keyword(s):  
Cyclic Peptide ◽  
Protecting Groups ◽  
Polymer Conjugates ◽  
Synthetic Strategy ◽  
Active Ester ◽  
Ester Aminolysis

A synthetic strategy for the preparation of cyclic peptide disulfide–polymer conjugates that does not require peptide protecting groups is reported.

scholarly journals Semisynthetic analogues of insulin. The use of N-substituted derivatives of methionine as acid-stable protecting groups

1977 ◽  
Vol 165 (3) ◽  
pp. 479-486 ◽  
Author(s):  
Derek J. Saunders ◽  
Robin Offord
Keyword(s):  
Protecting Groups ◽  
Amino Groups ◽  
Fat Cell ◽  
Selective Protection ◽  
Acid Cleavage ◽  
Active Ester ◽  
Cleavage Step ◽  
Cell Test ◽  
Derivatives Of ◽  
Acid Stable

1. We describe the use of benzyloxycarbonylmethionine and ethoxycarbonylmethionine for the selective protection of the amino groups of glycine-A1 and lysine-B29 of pig insulin. We have used the Edman method to remove residues from the N-terminal and of the B-chain of the NA1NB29-di-protected derivatives. The benzyloxycarbonyl group shows slight but noticeable lability in the acid-cleavage step, but the ethoxycarbonyl group remained intact even after five cycles of degradation. 2. We have prepared the following truncated forms of insulin via the di(ethoxycarbonylmethionyl) derivative: des-PheB1-insulin;des-(PheB1-ValB2)-insulin; des-(PheB1-ValB2-AsnB3)-insulin;des- (PheB1-ValB2-AsnB3-GlnB4)-insulin; des-(PheB1-ValB2-AsnB3 -GlnB4-HisB5)-insulin. 3. Insulin was re-synthesized from the di-protected des-PheB1-insulin by reaction with an active ester of t-butoxycarbonyl-l-phenylalanine. The product after deprotection crystallized, and the immunoreactivity of the crystalline material was identical with that of the native protein. 4. We have prepared the following analogues of insulin in a similar manner: [l-AlaB1]insulin; [l-ValB1]insulin; [l-TyrB1]insulin; [m-F-l-PheB1]insulin; [o-F-l-PheB1]-insulin; [o-F-l-PheB2]des-PheB1-insulin. All had between 34 and 62% of the activity of insulin in the fat-cell test. 5. We have also investigated the use of the benzyol, toluene-p-sulphonyl, p-nitrobenzyloxycarbonyl and 2,4-dinitrophenyl groups for the N-protection of the methionine active esters. Each should have had some particular advantage over the benzyloxycarbonyl and ethoxycarbonyl groups, but all proved in practice to have disadvantages that more than outweighed anything in their favour.

Visible Light-Mediated Oxidative Debenzylation

2020 ◽  
Author(s):  
Cristian Cavedon ◽  
Eric T. Sletten ◽  
Amiera Madani ◽  
Olaf Niemeyer ◽  
Peter H. Seeberger ◽  
...  
Keyword(s):  
Reaction Time ◽  
Visible Light ◽  
Functional Groups ◽  
Continuous Flow ◽  
Protecting Groups ◽  
Benzyl Ether ◽  
Complex Molecules ◽  
Protective Groups ◽  
Benzyl Ethers ◽  
Harsh Conditions

Protecting groups are key in the synthesis of complex molecules such as carbohydrates to distinguish functional groups of similar reactivity. The harsh conditions required to cleave stable benzyl ether protective groups are not compatible with many other protective and functional groups. The mild, visible light-mediated debenzylation disclosed here renders benzyl ethers orthogonal protective groups. Key to success is the use of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) as stoichiometric or catalytic photooxidant such that benzyl ethers can be cleaved in the presence of azides, alkenes, and alkynes. The reaction time for this transformation can be reduced from hours to minutes in continuous flow. <br>

Endgroup and Sidechain Functionalization of Surface-Initiated ROMP Thin Films: Progress Towards ROMP-Based Molecular Wires

2018 ◽  
Author(s):  
Nicholas Marshall
Keyword(s):  
Thin Films ◽  
Contact Angle ◽  
Cyclic Voltammetry ◽  
Polymer Films ◽  
Conjugated Polymer ◽  
Ring Opening ◽  
Molecular Wires ◽  
Metathesis Polymerization ◽  
Cross Metathesis ◽  
Active Ester

A set of experiments in surface-initiated ring-opening metathesis polymerization, including end-functionalization of growing brushes and contact angle/cyclic voltammetry measurements. We report preparation and CV of two different conjugated polymer films, and several endgroup and sidechain functionalization experiments using cross-metathesis and active ester substitution.<br>

A Facile, Efficient and Selective Deprotection of P - Methoxy Benzyl Ethers Using Zinc (II) Trifluoromethanesulfonate

2019 ◽  
Vol 16 (12) ◽  
pp. 955-958
Author(s):  
Reddymasu Sireesha ◽  
Reddymasu Sreenivasulu ◽  
Choragudi Chandrasekhar ◽  
Mannam Subba Rao
Keyword(s):  
Room Temperature ◽  
Protecting Groups ◽  
Side Reactions ◽  
Reaction Conditions ◽  
Acid Sensitivity ◽  
Time Period ◽  
Protective Groups ◽  
Benzyl Ethers ◽  
Last Stage ◽  
Zinc Triflate

: Deprotection is significant and conducted over mild reaction conditions, in order to restrict any more side reactions with sensitive functional groups as well as racemization or epimerization of stereo center because the protective groups are often cleaved at last stage in the synthesis. P - Methoxy benzyl (PMB) ether appears unique due to its easy introduction and removal than the other benzyl ether protecting groups. A facile, efficient and highly selective cleavage of P - methoxy benzyl ethers was reported by using 20 mole% Zinc (II) Trifluoromethanesulfonate at room temperature in acetonitrile solvent over 15-120 min. time period. To study the generality of this methodology, several PMB ethers were prepared from a variety of substrates having different protecting groups and subjected to deprotection of PMB ethers using Zn(OTf)2 in acetonitrile. In this methodology, zinc triflate cleaves only PMB ethers without affecting acid sensitivity, base sensitivity and also chiral epoxide groups.

Hafnium(IV) Chloride Catalyzes Highly Efficient Acetalization of Carbonyl Compounds

2019 ◽  
Vol 16 (6) ◽  
pp. 913-920 ◽  
Author(s):  
Israel Bonilla-Landa ◽  
Emizael López-Hernández ◽  
Felipe Barrera-Méndez ◽  
Nadia C. Salas ◽  
José L. Olivares-Romero
Keyword(s):  
Microwave Heating ◽  
Reaction Times ◽  
Protecting Groups ◽  
Catalyst Loading ◽  
Selective Protection ◽  
Highly Efficient ◽  
Aldehydes And Ketones ◽  
High Yields ◽  
Novel Catalyst ◽  
Acid Labile

Background: Hafnium(IV) tetrachloride efficiently catalyzes the protection of a variety of aldehydes and ketones, including benzophenone, acetophenone, and cyclohexanone, to the corresponding dimethyl acetals and 1,3-dioxolanes, under microwave heating. Substrates possessing acid-labile protecting groups (TBDPS and Boc) chemoselectively generated the corresponding acetal/ketal in excellent yields. Aim and Objective: In this study. the selective protection of aldehydes and ketones using a Hafnium(IV) chloride, which is a novel catalyst, under microwave heating was observed. Hence, it is imperative to find suitable conditions to promote the protection reaction in high yields and short reaction times. This study was undertaken not only to find a novel catalyst but also to perform the reaction with substrates bearing acid-labile protecting groups, and study the more challenging ketones as benzophenone. Materials and Methods: Using a microwave synthesis reactor Monowave 400 of Anton Paar, the protection reaction was performed on a raging temperature of 100°C ±1, a pressure of 2.9 bar, and an electric power of 50 W. More than 40 substrates have been screened and protected, not only the aldehydes were protected in high yields but also the more challenging ketones such as benzophenone were protected. All the products were purified by simple flash column chromatography, using silica gel and hexanes/ethyl acetate (90:10) as eluents. Finally, the protected substrates were characterized by NMR 1H, 13C and APCI-HRMS-QTOF. Results: Preliminary screening allowed us to find that 5 mol % of the catalyst is enough to furnish the protected aldehyde or ketone in up to 99% yield. Also it was found that substrates with a variety of substitutions on the aromatic ring (aldehyde or ketone), that include electron-withdrawing and electrondonating group, can be protected using this methodology in high yields. The more challenging cyclic ketones were also protected in up to 86% yield. It was found that trimethyl orthoformate is a very good additive to obtain the protected acetophenone. Finally, the protection of aldehydes with sensitive functional groups was performed. Indeed, it was found that substrates bearing acid labile groups such as Boc and TBDPS, chemoselectively generated the corresponding acetal/ketal compound while keeping the protective groups intact in up to 73% yield. Conclusion: Hafnium(IV) chloride as a catalyst provides a simple, highly efficient, and general chemoselective methodology for the protection of a variety of structurally diverse aldehydes and ketones. The major advantages offered by this method are: high yields, low catalyst loading, air-stability, and non-toxicity.

[1-β-Mercaptopropionic acid, 8-norarginine]vasopressin and [1-β-mercaptopropionic acid, 8-D-norarginine]vasopressin. Two analogs with strong biological effects

1979 ◽  
Vol 44 (4) ◽  
pp. 1179-1186 ◽  
Author(s):  
Milan Zaoral ◽  
František Brtník ◽  
Martin Flegel ◽  
Tomislav Barth ◽  
Alena Machová
Keyword(s):  
Biological Effects ◽  
Disulfide Bridge ◽  
Protecting Groups ◽  
Pressor Effect ◽  
Amino Groups ◽  
Mercaptopropionic Acid ◽  
Antidiuretic Effect ◽  
Carbodiimide Method

[1-β-Mercaptopropionic acid, 8-norarginine]vasopressin (L8, D8; I, II) was prepared by condensation of β-benzylthiopropionyl-tyrosyl-phenylalanyl-glutaminyl-asparaginyl-S-benzylcysteine with Nγ-benzyloxycarbonyl-α,γ-diaminobutyryl-glycine amide (L2, D2) by the azide or carbodiimide method, respectively, removal of the benzyloxycarbonyl residue, guanidination of γ-amino groups, removal of protecting groups, closing of the disulfide bridge, and electrophoretic purification. I has an almost 2 times higher antidiuretic effect than DDAVP and a 3 times higher pressor effect than AVP. II has 20-25% of the antidiuretic effect of DDAVP and 16 IU/mg of the pressor effect.

Vasopressin and oxytocin analogs with interchanged sequence of amino acids in positions 7 and 8. synthesis and biological effects

1981 ◽  
Vol 46 (9) ◽  
pp. 2136-2139 ◽  
Author(s):  
Ivo Bláha ◽  
Viktor Krchňák ◽  
Milan Zaoral
Keyword(s):  
Amino Acids ◽  
Solid Phase Synthesis ◽  
Solid Phase ◽  
Biological Effects ◽  
Free Flow ◽  
Protecting Groups ◽  
Pressor Effect ◽  
Phase Synthesis ◽  
Antidiuretic Effect

p-Toluenesulfonyl-S-benzylcysteinyl-tyrosyl-phenylalanyl-glutaminyl-asparaginyl-S-benzylcysteinyl-NG-p-toluenesulfanylarginyl-prolyl-glycineamide (I) and S-benzylcysteinyl-tyrosyl-isoleucyl-glutaminyl-asparaginyl-S-benzylcysteinyl-leucyl-prolyl-glycine amide (III) were prepared by solid phase synthesis. After removal of the protecting groups, closure of the disulfide ring, and purification by continuous free-flow electrophoresis [arginine7, proline8]vasopressin (II) and [leucine7, proline8]oxytocin (IV) were obtained. The antidiuretic effect of II is markedly higher than its pressor effect; IV possesses c. 6% of the uterotonic and c. 10% of the galactogogous effect of oxytocin.

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