Jie jack li the third edition contains major improvements over the previous edition. Pummerer reaction an overview sciencedirect topics. Oct 11, 2017 the pummerer rearrangement, whereby sulfoxides react with electrophiles to give. Compound 3 undergoes elimination to produce the thionium ion 4.
Aromatic metamorphosis of heteroarenes by precisely designed catalysts. The pummerer rearrangement has been widely studied and has received considerable attention as a synthetically useful process. Types of chemical reactions in inorganic chemistry inorganic chemical reactions are common types in chemistry, and there are only four basic types of reactions in chemistry, but some websites i found they categorize many types as they are the basic types, no. Dual vicinal functionalisation of heterocycles via an. The pummerer rearrangement is an organic reaction whereby an alkyl sulfoxide rearranges to. The mechanism of the pummerer rearrangement begins with the acylation of the sulfoxide. Wikimedia commons has media related to rearrangement reactions this category is part of a classification scheme based on the royal society of chemistry reaction names ontology, compiled by colin bachelor, celia gitterman and david barden.
Application of the pummerer reaction toward the synthesis of. Summary the pummerer rearrangement, also called the pummerer. Pummerer rearrangement sulfurstabilized cations chemtube3d. Pummerer rearrangement results in oxidation of the carbon atom adjacent to the sulfoxide group at the same time the sulfoxide is reduced to sulfide. A direct conversion of carboxylic acids to methylthiomethyl esters using a microwaveassisted pummerer rearrangement with dimethylsulfoxide.
In recent years, many exciting advances have demonstrated the broad scope and synthetic utility of pummerer methodology and the versatility of thionium ion intermediates. Oct 02, 2015 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 pummerer rearrangement products, obtained from rc,rs. Different from other books on name reactions in organic chemistry, name reactions, a collection of detailed reaction mechanisms focuses on their mechanisms. Masakatsu shibasaki and coworkers at the university of tokyo have recently published in aciee on the total synthesis of enthyperforin, a polyprenylated acylphloroglucinol. One of the biosynthetic enzymes in serratia, pigb, and its homologue in hahella, hapb, are shown to be fad. This reaction was also applied to oxazolidine 211, furnishing the eightmembered ring 212 in 72% yield and with a 98% diastereoselectivity. Download full guide of types of chemical reactions in pdf, doc format. Emphasizes strategic synthetic planning and implementation. In addition to updated references, each reaction is now supplemented with two to three representative examples in synthesis. Molecular rearrangements in organic synthesis christian.
Intermolecular radical reaction of o,seacetals generated via. Molecular rearrangements in organic synthesis wiley. Interactive 3d chemistry animations of reaction mechanisms and 3d models of chemical structures for students studying university courses and advanced. Bridgehead sulfoxides were reacted under a variety of conditions to provide bridgehead. Mechanism, references and reaction samples of the pummerer rearrangement. To clarify the details of the sshift reactions, we. A pentacyclic model system featuring the trans azabicyclo3. The treatment of sulfoxides with acid anhydrides or acid chlorides brings about a reaction called the pummerer rearrangement, which gives. The key transformations of this sequence include a a pummerer reactionmediated oxidative bicyclization, and b a wolff rearrangementbased ring contraction to deliver the strained azabicyclo3.
All types of chemical reactions in organic and inorganic. Pdf bondforming and breaking reactions at sulfuriv. Examples of both inter and intramolecular reactions are now widespread, and strategies incor porating heteroatom or carbon nucleophiles have found broad. Various methyl sulfoxides were converted into the corresponding azidomethyl sulfides. This process is experimental and the keywords may be updated as the learning algorithm improves. The pummerer rearrangement is an organic reaction whereby an alkyl sulfoxide rearranges to an. Having implemented pummerer rearrangement on a sugar substrate, synthetic utility of the rearrangement product, namely vinyl. The acetate then acts as a catalyst to induce an elimination reaction to produce the cationicthial structure 4, with acetic acid as byproduct. These keywords were added by machine and not by the authors. The proton source for this last step is most likely the conjugate acid of the base used to generate the copperacetylide. Synthesis of a functionalized oxathiolane intermediate to antivirals such as the reverse transcriptase inhibitor 3tctm.
This study was undertaken to further explore and broaden their usefulness. The rearranged products can be hydrolyzed to give aldehydes. Procter cyclization heterocycles pummererreactionsulfur thionium ions 1. Bridgehead intermediates have only recently been employed in organic synthesis.
There are no examples of reactions of substituents attatched to ring oxygen atoms. The first crystal structure of a specific cyclic diester formed between a solvated boronic acid, located in the ligand pocket of an engineered lipocalin protein, and a cis. Pages in category rearrangement reactions the following 95 pages are in this category, out of 95 total. Introduction the substrate of the classical pummerer reaction1 is an. Aug 29, 2012 while the pummerer rearrangement has been known in the literature for over one hundred years, 6 to our knowledge, there are no reports of a pummerer reaction on dmso to functionalize carboxylic acids using a microwaveassisted protocol. Provides ready access to the genesis, mechanisms, and synthetic utility of rearrangement reactions. Files are available under licenses specified on their description page. Even though the sugardiol binding activity of boric acid and its derivatives has been known for almost a century, structural information on corresponding complexes has remained scarce up to now.
Molecular rearrangements in organic synthesis christian m. An important name reaction with versatility in organic synthesis. The pummerer reaction of sulfinyl compounds lucchi. Supporting information intermolecular radical reaction of o,seacetals generated via selenopummerer rearrangement daisuke urabe, hiroki yamaguchi, ayumi someya, and masayuki inoue. The reaction can also be described as an internal redox process where the s x group is reduced and the.
The mechanism of the pummerer rearrangement begins with the acylation of the sulfoxide 1 and 2. The pummerer reaction acs publications american chemical. All structured data from the file and property namespaces is available under the creative commons cc0 license. The method utilizes readily available coupling partners, has broad scope and by virtue of the facile interrupted pummerer reaction and charge accelerated 3,3. Intermolecular radical reaction of o,seacetals generated. A novel method for the synthesis of azidomethyl sulfides by pummerer rearrangement using bispnitrophenyl phosphorazidate pno 2 dppa as an azidation reagent was developed. The detailed mechanism is provided for each of them and several samples are given to illustrate their synthetic usefulness.
Biographical sketches for the chemists who discovered or developed those name reactions have been included. Pummererrearrangements are wellknown to organic sulfur chemists to yield internal redox products from c,hacidic sulfoxides including desoxygenation of. All types of chemical reactions in organic and inorganic chemistry by examples. Name reactions a collection of detailed mechanisms and. Prodigiosin has long caught researchers eyes due to its bright red colour. Supporting information intermolecular radical reaction of o,seacetals generated via seleno pummerer rearrangement daisuke urabe, hiroki yamaguchi, ayumi someya, and masayuki inoue. Furthemore, the subject index is significantly expanded. The resulting sulfoxide was allowed to undergo pummerer rearrangement to afford vinyl sulfide scheme 4, resulting from the elimination of hoac in the thioacetal formed in situ. The key transformations of this sequence include a a pummerer reactionmediated oxidative bicyclization, and b a wolff rearrangement based ring contraction to deliver the strained azabicyclo3. The pummerer reaction involves the formation of an functionalized sulfide from a sulfoxide bearing at least one hydrogen atom. Rearrangement of 68 then provides the copper enolate of the corresponding. A shopkeeper sells a file and a notebook for rs 27 to the first customer, a notebook and a pen for rs 31 to the second customer and a pen and file for rs 29 to the third customer.
Therefore, sulfoxides and sulfides can be considered as aldehyde precursors. Vicarious nucleophilic aromatic substitution via trapping. Sep 07, 2017 an important name reaction with versatility in organic synthesis. Additive and vinylogous pummerer reactions of amido sulfoxides and their use in the preparation of nitrogen containing heterocycles. Download acrobat pdf file 2mb supplementary data 1. The reactions of ocarboxyphenyl sulfoxides 95 and sulfoxide 115 encountered earlier schemes 21 and 26 are examples of the additive pummerer reaction. Synthesis of nitrogen heterocycles using the intramolecular. Acetate adds to the sulfonium ion to give the final product 5. Original papers coppercatalyzed twofold silylmetalation of alkynes. The mechanism of the pummerer rearrangement begins with the acylation of the sulfoxide resonance structures 1 and 2 by acetic anhydride to give 3, with acetate as byproduct.
Posts about pummerer rearrangement written by naturalproductman. Included are several functional group equivalents considered to be at the same oxidation state. Reaction of pummerer rearrangement intermediate with thiols. Jun 18, 2007 that a 2,3sigmatropic rearrangement occurs, as opposed to a stevens rearrangement, was established by treating 207b with ich 2 2 zn followed by nbuli to produce 210b in 76% yield. The mechanism of pummerer rearrangement has been investigated using. The mechanism of the pummerer rearrangeme nt begins with the acylation of the sulfoxide resonance structures 1 and 2 by acetic anhydride to give 3, with acetate as byproduct. Type reactions as powerful tools in organic synthesis. The utilization of bridgehead intermediates in organic. Pummerer reaction of indole2sulfoxides or sulfides bearing.
Pummerer rearrangement purdie methylation, irvinepurdie methylation quelet reaction. This is illustrated by the progression of a methyl group to a carboxylic acid in a series of 2electron oxidations, as shown at right. 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. A direct conversion of carboxylic acids to methylthiomethyl. Roland heinrich scholl born in switzerland in 1865 his career spanned 5 universities around europe and 2 world wars. In this reaction, sulfur is reduced while adjacent carbon is oxidized. The sulfinatesulfone pummerer rearrangement publikationen. The pummerer rearrangement and successive cyclisation with either the intramolecular cc double bond or the pyrrole were unsuccessful. The reaction operates under mild, metal free conditions and without directing groups, via an interrupted pummerer coupling of activated allyl sulfoxides, generating allyl heteroaryl sulfonium salts that are predisposed to a charge accelerated 3,3sigmatropic rearrangement. Reactions enzymeinduced elimination of sulfenic acids. Molecular rearrangements in organic synthesis wiley online.
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