Favorskii rearrangement is one the important reactions in organic chemistry. Molecular rearrangements in organic synthesis edition 1. These themes support effective and efficient synthetic. The demjanov and tiffeneaudemjanov ring expansions. The potential of the oxyfavorskii rearrangement to form branched cisfused bicyclic ethers was explored. An informational video about the named chemical reaction, the favorskii rearrangment. Favorskii rearrangement an overview sciencedirect topics. Reaction mechanisms in organic chemistry by mukul c. This book summarizes 100 essential mechanisms in organic chemistry ranging from classical such as the reformatsky reaction from 1887 to recently elucidated mechanism such as the coppericatalyzed alkyneazide cycloaddition. Provides ready access to the genesis, mechanisms, and synthetic utility of rearrangement reactions. You are always encouraged to read books and take final decision by your own. The reaction was discovered in the early 1900s by the russian chemist alexei yevgrafovich favorskii.
Let us have some prior understanding of its mechanism and its applications. The reactions are easy to grasp, wellillustrated and underpinned with explanations and additional information. As depicted in the following diagram, this reaction is believed to proceed by way of a cyclopropanone intermediate. Summary consideration of the mechanism of the quasi. Flavinmediated dual oxidation controls an enzymatic favorskiitype rearrangement. Halogenated ketone undergoes rearrangement in the presence of a base like hydroxide, alkoxide or amine to give a carboxylic acid or its derivative i. Definition references favorskii rearrangement the basecatalysed rearrangement of. Name reactions and reagents in organic synthesis, second edition, pp. Please note that the content of this book primarily consists of articles available from wikipedia or other free sources online. Provides ready access to the genesis, mechanisms, and synthetic utility of rearrangement reactions emphasizes strategic synthetic planning and implementation covers 20 different. The demjanov rearrangement is the chemical reaction of primary amines with nitrous acid to give rearranged alcohols. Wolff rearrangement an overview sciencedirect topics. Comprehensive organic synthesis 2nd edition elsevier.
The second edition of comprehensive organic synthesiswinner of the 2015 prose award for multivolume referencescience from the association of american publishersbuilds upon the highly respected first edition in drawing together the new common themes that underlie the many disparate areas of organic chemistry. This is not a text book but a reference book supplement to the text of organic chemistry meant for university students. Favorskii rearrangement of some abromoketones by nicholas j. Name reactions a collection of detailed mechanisms and. Calculate the sound power the energy per second incident on an eardrum at a the threshold of hearing and b the threshold of pain. The favorskii rearrangement, named for the russian chemist alexei yevgrafovich favorskii, is most principally a rearrangement of cyclopropanones and.
Nazarov cyclization reaction, sigmatropic reaction, tiffeneaudemjanov rearrangement, alphaketol rearrangement, electrocyclic reaction, claisen rearrangement, beckmann rearrangement, arndteistert reaction, dipimethane rearrangement. Favorskii rearrangement and quasifavorskii rearrangement third expanded edition. The arrangement of cyclic ketones involves ring contraction ahluwalia. Regardless of the controversial history underlying certain named reactions, it is. Stereoselective favorskii rearrangement of carvone. Favorskii rearrangement comprehensive organic name. Stereochemically probing the photo favorskii rearrangement. Very important name reaction for any competitive examination like csirnet, gate, iitjam, tifr, barc, ongc etc.
Favorskii rearrangement and quasi favorskii rearrangement. Methanol and primary amines were effective nucleophiles for the rearrangement. Flavinmediated dual oxidation controls an enzymatic. Favorskii reaction an overview sciencedirect topics. A new mechanism for the favorskii rearrangement organic. Emphasizes strategic synthetic planning and implementation. In favorskii rearrangement, the esters are formed if alkoxides are used as. Stereochemistry of favorskii rearrangement of chloromethyl ketones. It is named after the russian chemist nikolai jakovlevich. As in previous editions, each reaction is delineated by its detailed stepbystep, electronpushing mechanism and supplemented with the original and the latest references, especially from. Organic reactions volumes acs division of organic chemistry.
The favorskii rearrangement is the base catalyzed rearrangement of enolizable. Both tertiary and quaternary centers were constructed in highly stereospecific manners. The book illustrates the stepwise mechanisms of each reaction, making it an excellent teaching tool for undergraduates. The favorskii rearrangement is a baseinduced rearrangement of. It involves substitution by a hydroxyl group with a possible ring expansion. Comprehensive organic synthesisdraws together the common themes that underlie the many apparently disparate areas of organic chemistry which underpin synthetic strategies, thus providing a comprehensive overview of this important discipline. When this rearrangement is catalyzed by an acid, it is called meyerschuster rearrangement.
In this video, weve learned about very much for important rearrangement reaction. The journal of organic chemistry 20, 78 5, 17181729. Our synthetic efforts made use of a favorskii rearrangement based on the literature precedent to convert a carvonederived cyclohexanone substrate into a highly functionalized cyclopentyl aldehyde. The suitability of a given reaction for an unknown application is best judged from the. Methylation evans chiral tvacyloxazolidinone methodology evanstischenko reaction favorskii rearrangement.
Favorskii rearrangement is simply a tertiary or quaternary carbon embedded in a polycyclic carbon framework. These synthetic strategies are illustrated with examples in the chapter. Each entry describes all available web materials for the reaction of interest. The rearrangement of cyclopropanones, often obtained as intermediates from the basecatalyzed reaction of. Designed for practitioners of organic synthesis, this book helps chemists understand and take advantage of rearrangement reactions to enhance the synthesis of useful chemical compounds. The catalytic, enantioselective favorskii reaction. Favorskii rearrangement quickly reveals that there are a number of related reactions.
An example of this isomerization is the acidic hydrolysis of an borneoltype substance to give camphenelike structures, the wm rearrangement camphene rearrangement type i and the nametkin isomerization camphene rearrangement type ii products respectively. Molecular rearrangements in organic synthesis organic. The mentioned rearrangement plays a key role in many total synthesis due to the fact that important modifications in the structure of the substrate occur during the process. The contributions have been organized to reflect the way in which synthetic chemists approach a problem. The second key fragment in our synthesis was a functionalized allylboron reagent. The favorskii rearrangement not to be confused with the favorskii reaction, named for the russian chemist alexei yevgrafovich favorskii, is most principally a rearrangement of cyclopropanones and. Gagosian chemistry department, columbia university, new york, new york 10027 christoffer rappe and leif knutsson institute of chemistry, university of uppsala, uppsala, sweden the baseinduced rearrangement of ahalogenoketones to. Favorskii rearrangement and quasifavorskii rearrangement.
Photochemical wolff rearrangement of 4diazoacetylphenol in cd 3 cnd 2 o gives ketene 63 as the primary product, leading to deuterated 4hydroxyphenylacetic acid eqn 4. The favorskii reaction is an organic chemistry reaction between an alkyne and a carbonyl group, under a basic condition. Each reaction is delineated by its detailed stepbystep, electronpushing mechanism, supplemented with the original and the latest references. A manual for csirugc national eligibility test for lectureship and jrfnamed reactions. It covers over 300 classical as well as contemporary name reactions. Stereochemistry of favorskii rearrangement of chloromethyl. Scheme 1 a favorskii rearrangement of an aliphatic ketone. Interested in mechanistic problems, nmr and scientific cheminfographics.
When the carbonyl is an aldehyde, a rearrangement occurs and leads to an enone. The favorskii rearrangement, named for the russian chemist alexei yevgrafovich favorskii. Arylation of unsaturated compounds by diazonium salts. Stereocontrolled synthesis of substituted bicyclic ethers. In this fifth edition of jack jie lis seminal name reactions, the author has added twentyseven new name reactions to reflect the recent advances in organic chemistry. Molecular rearrangements in organic synthesis wiley. Acetates through a novel intermediate and an unexampled mechanistic pathway. Pages in the full organic reactions chapters category contain bibliographic information for currently published organic reactions chapters. The phydroxyphenacyl group 1 is an effective photoremovable protecting group, because it undergoes an unusual photofavorskii rearrangement concomitant with the fast release vladimir andreevich born mar. Stereoselective favorskii rearrangement of carvone chlorohydrin. Graduate research symposium grs grs history national organic chemistry.
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