Supporting information intermolecular radical reaction of o,seacetals generated via seleno pummerer rearrangement daisuke urabe, hiroki yamaguchi, ayumi someya, and masayuki inoue. 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. Pummererrearrangements are wellknown to organic sulfur chemists to yield internal redox products from c,hacidic sulfoxides including desoxygenation of. 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 acetate then acts as a catalyst to induce an elimination reaction to produce the cationicthial structure 4, with acetic acid as byproduct. The pummerer reaction of sulfinyl compounds lucchi.
The reactions of ocarboxyphenyl sulfoxides 95 and sulfoxide 115 encountered earlier schemes 21 and 26 are examples of the additive pummerer reaction. The pummerer reaction involves the formation of an functionalized sulfide from a sulfoxide bearing at least one hydrogen atom. The pummerer reaction acs publications american chemical. The reaction can also be described as an internal redox process where the s x group is reduced and the. The treatment of sulfoxides with acid anhydrides or acid chlorides brings about a reaction called the pummerer rearrangement, which gives. Pages in category rearrangement reactions the following 95 pages are in this category, out of 95 total. In addition to updated references, each reaction is now supplemented with two to three representative examples in synthesis. A direct conversion of carboxylic acids to methylthiomethyl esters using a microwaveassisted pummerer rearrangement with dimethylsulfoxide. The pummerer rearrangement products, obtained from rc,rs. Masakatsu shibasaki and coworkers at the university of tokyo have recently published in aciee on the total synthesis of enthyperforin, a polyprenylated acylphloroglucinol. This reaction was also applied to oxazolidine 211, furnishing the eightmembered ring 212 in 72% yield and with a 98% diastereoselectivity. Included are several functional group equivalents considered to be at the same oxidation state.
A novel method for the synthesis of azidomethyl sulfides by pummerer rearrangement using bispnitrophenyl phosphorazidate pno 2 dppa as an azidation reagent was developed. Reactions enzymeinduced elimination of sulfenic acids. Procter cyclization heterocycles pummererreactionsulfur thionium ions 1. Intermolecular radical reaction of o,seacetals generated. The mechanism of pummerer rearrangement has been investigated using. All structured data from the file and property namespaces is available under the creative commons cc0 license. Supporting information intermolecular radical reaction of o,seacetals generated via selenopummerer rearrangement daisuke urabe, hiroki yamaguchi, ayumi someya, and masayuki inoue. This study was undertaken to further explore and broaden their usefulness. The rearranged products can be hydrolyzed to give aldehydes. There are no examples of reactions of substituents attatched to ring oxygen atoms.
The journal of organic chemistry 1998, 63 , 42564268. Mechanism, references and reaction samples of the pummerer rearrangement. Acetate adds to the sulfonium ion to give the final product 5. 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. The detailed mechanism is provided for each of them and several samples are given to illustrate their synthetic usefulness. Sep 07, 2017 an important name reaction with versatility in organic synthesis. 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. All types of chemical reactions in organic and inorganic.
Molecular rearrangements in organic synthesis wiley online. Molecular rearrangements in organic synthesis christian m. Pummerer reaction an overview sciencedirect topics. The mechanism of the pummerer rearrangement begins with the acylation of the sulfoxide.
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 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. The pummerer rearrangement has been widely studied and has received considerable attention as a synthetically useful process. One of the biosynthetic enzymes in serratia, pigb, and its homologue in hahella, hapb, are shown to be fad. Intermolecular radical reaction of o,seacetals generated via. Vicarious nucleophilic aromatic substitution via trapping. The conversion of the1,2dithiolium cation 72 into the isothiazoles 76 via the action of ammonia has been demonstrated. Files are available under licenses specified on their description page. 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. 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. This process is experimental and the keywords may be updated as the learning algorithm improves. Synthesis of a functionalized oxathiolane intermediate to antivirals such as the reverse transcriptase inhibitor 3tctm. Furthemore, the subject index is significantly expanded. The pummerer rearrangement and successive cyclisation with either the intramolecular cc double bond or the pyrrole were unsuccessful.
Roland heinrich scholl born in switzerland in 1865 his career spanned 5 universities around europe and 2 world wars. The pummerer rearrangement is an organic reaction whereby an alkyl sulfoxide rearranges to. Summary the pummerer rearrangement, also called the pummerer. These keywords were added by machine and not by the authors. Molecular rearrangements in organic synthesis christian. This is illustrated by the progression of a methyl group to a carboxylic acid in a series of 2electron oxidations, as shown at right. In this reaction, sulfur is reduced while adjacent carbon is oxidized. Introduction the substrate of the classical pummerer reaction1 is an. An important name reaction with versatility in organic synthesis. Therefore, sulfoxides and sulfides can be considered as aldehyde precursors. The mechanism of the pummerer rearrangement begins with the acylation of the sulfoxide 1 and 2.
Recent developments in thionium ion chemistry laura h. The method utilizes readily available coupling partners, has broad scope and by virtue of the facile interrupted pummerer reaction and charge accelerated 3,3. 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. Emphasizes strategic synthetic planning and implementation. Aromatic metamorphosis of heteroarenes by precisely designed catalysts. Reaction of pummerer rearrangement intermediate with thiols. Pummerer sulfoxide rearrangement an overview sciencedirect. Jie jack li the third edition contains major improvements over the previous edition. Interactive 3d chemistry animations of reaction mechanisms and 3d models of chemical structures for students studying university courses and advanced. Rearrangement of 68 then provides the copper enolate of the corresponding. Additive and vinylogous pummerer reactions of amido sulfoxides and their use in the preparation of nitrogen containing heterocycles. Application of the pummerer reaction toward the synthesis of.
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. In recent years, many exciting advances have demonstrated the broad scope and synthetic utility of pummerer methodology and the versatility of thionium ion intermediates. Pdf bondforming and breaking reactions at sulfuriv. To clarify the details of the sshift reactions, we. Bridgehead intermediates have only recently been employed in organic synthesis. All types of chemical reactions in organic and inorganic chemistry by examples. Pummerer reaction of indole2sulfoxides or sulfides bearing. A pentacyclic model system featuring the trans azabicyclo3. Examples of both inter and intramolecular reactions are now widespread, and strategies incor porating heteroatom or carbon nucleophiles have found broad. Type reactions as powerful tools in organic synthesis. Biographical sketches for the chemists who discovered or developed those name reactions have been included. Bridgehead sulfoxides were reacted under a variety of conditions to provide bridgehead.
Molecular rearrangements in organic synthesis wiley. Synthesis of nitrogen heterocycles using the intramolecular. Oct 11, 2017 the pummerer rearrangement, whereby sulfoxides react with electrophiles to give. The pummerer rearrangement is an organic reaction whereby an alkyl sulfoxide rearranges to an.
Download full guide of types of chemical reactions in pdf, doc format. 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. The sulfinatesulfone pummerer rearrangement publikationen. 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. Different from other books on name reactions in organic chemistry, name reactions, a collection of detailed reaction mechanisms focuses on their mechanisms.
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. Having implemented pummerer rearrangement on a sugar substrate, synthetic utility of the rearrangement product, namely vinyl. Pummerer rearrangement sulfurstabilized cations chemtube3d. Provides ready access to the genesis, mechanisms, and synthetic utility of rearrangement reactions. Compound 3 undergoes elimination to produce the thionium ion 4. 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. Recent developments in chiral nonracemic sulfinylgroup. Pummerer rearrangement results in oxidation of the carbon atom adjacent to the sulfoxide group at the same time the sulfoxide is reduced to sulfide. The utilization of bridgehead intermediates in organic. A direct conversion of carboxylic acids to methylthiomethyl. Dual vicinal functionalisation of heterocycles via an. Prodigiosin has long caught researchers eyes due to its bright red colour. Various methyl sulfoxides were converted into the corresponding azidomethyl sulfides.
Pummerer rearrangement purdie methylation, irvinepurdie methylation quelet reaction. Posts about pummerer rearrangement written by naturalproductman. The venerable pummerer rearrangement is perhaps the most. Original papers coppercatalyzed twofold silylmetalation of alkynes. Name reactions a collection of detailed mechanisms and. 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. This page was last edited on 26 october 2018, at 11.
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