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. Terminal alkyne protecting groups in organic synthesis. Purified, individual amino acids used to synthesize peptides are reacted with these protecting groups prior to synthesis, and then specific protecting groups are removed from the newly added amino acid a step called deprotection just after coupling to allow the next incoming amino acid to bind to the growing peptide chain in the proper. Protection and deprotection of functional groups in organic. Thioethers are in general formed by reaction of the thiol, in a basic solution, with a halide. A protecting group must fulfill a number of requirements. Oligonucleotide synthesis is the chemical synthesis of relatively short fragments of nucleic acids with defined chemical structure. Organic synthesismeans the same as synthetic organic chemistry. Protein synthesis is important for several reasons including. Protection and deprotection of functional groups in. These protection groups prevent unwanted side reactions and force the formation of the desired product during synthesis figure 3. It has been replaced in most labs by solidphase synthesis see below.
Kocienski, protecting groups, georg thieme verlag, 1994 1. Qualities of a good protecting group 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. Protection for the carbonyl group protective groups in. Retrosynthetic approch to organic synthesis protecting groups dr. In this discussion let us focus on the classes of protecting groups.
Carboxylic acids protect functional groups which may be incompatible with a set of reaction conditions. First, a phorphoramidite is a normal nucleotide but with protection groups, such as a trityl group, added to its reactive amine, hydroxyl, and phosphate groups. However, it retains usefulness in largescale production of peptides for industrial purposes. The use of this dmtrcontaining protecting group enabled us to estimate colorimetrically the amount of the m 2 2,2 g residue that was incorporated into the. Introducing, removing or transforming functional groups in a fashion that achieves the functionality of the desired. Protect functional groups which may be incompatible with a set of reaction. Theyll give your presentations a professional, memorable appearance the kind of sophisticated look that todays audiences expect. Small solid beads, insoluble yet porous, are treated with. Protecting groups contemporary organic synthesis rsc. This volume provides, at postgraduate student level, an accessible introduction to a topic of central importance in organic synthesis. Amines are the most widely used functional group in solidphase organic chemistry.
It plays an important role in multistep organic synthesis. It plays an important role in multistep organic synthesis in many preparations of delicate organic compounds, some specific parts of their molecules cannot survive the required reagents or chemical environments. Worlds best powerpoint templates crystalgraphics offers more powerpoint templates than anyone else in the world, with over 4 million to choose from. Protecting groups in organic synthesis 6 the commonly encountered functional groups in organic synthesis that are reactive to nucleophilic or electrophilic reagents whose selective transformation may present challenges do regularly require deactivation by masking with a protecting group.
Nizami department of chemistry university of karachi slideshare uses cookies to improve functionality and performance, and to provide you with relevant advertising. Stability data for the most frequently used protective groups, protection and deprotection methods. Winner of the standing ovation award for best powerpoint templates from presentations magazine. As a consequence of the extensive application of heterogeneous catalysis in synthetic organic chemistry, a large number of articles describing. Protecting groups in solidphase organic synthesis acs. Protecting groups hydroxyl protecting groups 14 ethers 8. Protective groups in organic chemistry springerlink. Protecting groups in organic synthesis the qualities of a good protecting group 10 a good protecting group should be such that. Course objectives at the end of this course you should be able to. Protecting groups in organic synthesis1 ready protecting groups are a sad fact of synthetic chemistry they are usually needed, but rarely desired many syntheses have stalled because of trouble putting on or removing protecting groups 4 basic questions to address when choosing a p. Protection for the thiol group is important in many areas of organic research, particularly in peptide and protein syntheses that often involve the amino acid cysteine. Continuous hydrogenolysis of ndiphenylmethyl groups in a micropackedbed reactor.
Whereas enzymes synthesize dna and rna only in a 5 to 3 direction, chemical. I wish to convey my sincere regards and thanks to dr. An interesting alternative of the protecting group manipulations is the socalled unichemo strategy, 17,18 which was. Liquidphase peptide synthesis is a classical approach to peptide synthesis. From finite groups to lie groups universitext the organic chemistry of drug synthesis, volume 3 organic chemistry. A protecting group pg is a molecular framework that is introduced onto a specific functional group fg in a poly. Protection and deprotection of functional groups in organic synthesis by heterogeneous catalysis. Their stability against hydrolysis increases with the steric hindrance around the boronic acid ester conversely, there are cases where boronic acids are used to. The group is widely used in oligonucleotide synthesis. It covers the main functional groups requiring protection in organic synthesis, explaining why a particular protecting agent works and how an agent should be chosen. In addition, the nature of the protective group must be chosen carefully to ensure adequate stability throughout all the intermediary synthesis steps.
A multistep synthesis of any organic compound requires the chemist to accomplish three related tasks. G college, lucknow for her keen interest, encouragement and fruitful suggestions and for providing library facilities. Myers protective groups siliconbased protection of the. This is mainly due to the fact that nprotected amino acids are powerful and. Most common group for the protection of acid is ester. This course will largely be from class notes which will be available prior to the lecture. Constructing the carbon framework or skeleton of the desired molecule.
A protecting group is something that wont react under the conditions of a desired reaction, whereas the unprotected group would react. Moreover, the conditions for the protection and deprotection steps and the nature of the protective group itself mustnt interfere with other functional groups present in the molecule. Both the starting material and the product contain a benzene ring as the basic carbon skeleton. Wenjing hao, dan chen, yusen li, zongfan yang, guolong xing, juan li, long chen. The basic problem of peptide synthesis is one of protecting the amino group.
Derivatives of carbonyl compounds that have been used as protective groups in synthetic schemes are described in this chapter. There are links to pdf versions of the class notes below which can be read and printed. Thiols are also more nucleophilic than alcohols, especially in basic solution. A protecting group pg is a molecular framework that is introduced onto a specific functional group fg in a polyfunctional molecule to block its reactivity under reaction conditions needed to make modifications elsewhere in the molecule. Dithianes removed by metal salts or oxidizing agents. During the past decade there has been a great increase in the use of protective groups, especially in the synthesis of large and complex organic molecules. All of theses reactions are taken from our synthesis database and the list is continually growing. Ppt organic synthesis powerpoint presentation free to. Protective groups in organic synthesis download free epub. Giovanni sartori,roberto ballini,franca bigi,giovanna bosica,raimondo maggi,and paolo righi. Renu gupta, head department of chemistry lucknow christian p. Protecting groups for boronic acids chemstation int. Protecting an amine as a carbamate therefore enables other functional groups to undergo selective reactions with electrophiles whereby the carbamate protected amino group is left intact.
Protecting groups protection of carboxylic acids ch423courseonorganicsynthesis. Lets move on now to a discussion of protecting groups. There are nitrogencontaining groups attached to both molecules. Kocienski greenes protective groups in organic synthesis protective groups in organic synthesis groups and symmetries.
If i have two peptides and no protecting groups, i end up with a mess of four amino acids that can be a real pain to separate. The protecting group must be selectively removed in good yield by readily available reagents. However, two additional synthetic steps are needed to achieve this protection. Protecting groups in organic synthesis chemistry libretexts. The first page of this article is displayed as the abstract. Protecting groups an abbreviated representation of this synthesis is shown below.
Protecting groups for carboxylic acids are used to avoid reaction of the acidic cooh hydrogen with bases and nucleophiles or to prevent nucleophilic additions at the carbonyl carbon. Perhaps the greatest activity has been in the peptide field where such triumphs as the total synthesis of insulin and of bovine ribonuclease molecular weight,700 have been achieved. The protecting group reagent must react selectively kinetic chemoselectivity in good yield to give a protected substrate that is stable to the projected reactions. Ppt ethers powerpoint presentation free to download. Powerpoint presentations and answer keys are also available online to support instructors. Organic synthesis thousands of chemicals can be purchased, but millions of molecules are known. Select a protective group to get the conditions needed to installremove the group. Wuts, protective groups in organic synthesis 2nd edition j. Carbonyl protecting groups organic chemistry portal. Acetals and ketals are frequently utilized as protected groups of aldehydes and ketones, respectively, in organic synthesis and generally transformed into various functionalities via the acid. Since alcohols, aldehydes and ketones are the most frequently manipulated functional groups in organic synthesis, a great deal of work has appeared in their protection deprotection strategies. Functional group compatibility protecting groups 5. Protective groups in organic synthesis request pdf. The most comprehensive text on protecting groups there is.
The concept of protecting functional groups when a chemical reaction is to be carried out selectively at onereactive site in a multifunctional compound, other. Facile synthesis of porphyrin based covalent organic frameworks via an a2b2 monomer for highly efficient heterogeneous. Chem 220 a and b organic chemistry and preferably chem 220c or an equivalent course. Chemically stabilized phenylboranylidene groups having a. Greenes protective groups is a useful guide to the organic chemist, and the content is organized on the basis of the functional group to be protected i. Oh removal h 2 pdpph 3, phsih 3 2% n 2 h 4 stable basic and acidic conditions basic and acidic conditions basic and acidic conditions, hydrogenation orthogonal boc, fmoc, trt boc, fmoc, trt boc, fmoc, z, trt, alloc 4. The chemical synthesis of a molecule from a relatively simpler starting materials.
Several reaction samples of protection and deprotection are shown for each groups. Protecting groups list the organic synthesis database. The most useful protective groups are the acyclic and cyclic acetals or ketals, and the acyclic or cyclic thio acetals or ketals. When the most and second stable protecting groups were applied to the synthesis of m 2 2,2 g 5 ppt on controlled pore glass, the second stable protecting group showed the best result. Normally, the cleavage of acyclic acetals is easier than of cyclic acetals. The technique is extremely useful in current laboratory practice because it provides a rapid and inexpensive access to custommade oligonucleotides of the desired sequence. You wanna do some transformation on a molecule, and it would work so wonderfully if this other functional group wasnt on the molecule to screw it up.
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