Enediynes, enyneallenes, their reactions, and beyond smu. Enediynes undergo a bergman cyclization reaction to form the labile 1,4didehy drobenzene pbenzyne biradical. The bergman cyclization forms a 1,4benzenediyl diradical a highly reactive species, that reacts with a h donor to give the corresponding arenes. The wording over the last arrow reads proton donor. Bergman cyclization has shown strong impacts on a number of application fields including pharmaceutics,synthetic chemistry and material science. The bergman cyclization or bergman reaction or bergman cycloaromatization is an organic reaction and more specifically a rearrangement reaction taking place when an enediyne is heated in presence of a suitable hydrogen donor scheme 1. To find promising analogues of naturally occurring enediyne antibiotics with a sufficient reactivity in the bergman cyclization and moderately stable under isolation and storage, a scale of relative enediynes reactivity was created on the basis of calculated free activation energies for the bergman cyclization within 12 known and new benozothiophene, benzene, and cinnoline. The rutheniummediated cycloaromatization of acyclic trienes was accomplished in excellent yields. Quantum mechanics and molecular dynamic investigations of. Bc and related reactions find numerous practical applications, of which dna photocleavage is emphasized herein. Bergman cyclization is a chemical process during which highly reactive aryl diradicals are formed from enediyne precursors. An acyclic enediyne anticancer compound attributed to a. His discovery of the bergman cyclization was completed far in advance of the discovery of enediynes anticancer properties. Bergman cyclization, cheminform on deepdyve, the largest online rental service for scholarly research with thousands of academic publications available at your fingertips.
The bergman cyclization leads to the biradical 3, which adds to the. Intramolecular pericyclic reactions of acetylene derivatives. Cyclization definition and meaning collins english dictionary. This work describes mechanistic studies into a rutheniummediated cycloaromatization of dienynes. After completing his undergraduate studies in chemistry at carleton college in 1963, he received his ph. Jan 22, 2007 the design and activation of enediyne prodrugs that cleave dna upon bergman cyclization 1 remains a formidable synthetic challenge. This is a text widget, which allows you to add text or html to your sidebar. Results from nmr, raman scattering, photoluminescence and uv. Bergman cyclization, schreinerpascal cyclization, myerssaito cyclization, schmittel. Nov 01, 2011 bergman cyclization in polymer chemistry and material science bergman cyclization in polymer chemistry and material science xiao, yuli. Bergman professor of chemistry, ucberkeley the modern era of organotransition metal chemistry arguably began with the synthesis and. Request pdf an acyclic enediyne anticancer compound attributed to a bergman cyclization at physiological temperature enediyne cytotoxic drugs have. Files are available under licenses specified on their description page.
Chapters are organized according to the different cyclization intermediatescationic, radical, anionic, and metal complex intermediates. Rapid bergman cyclization of 1,2diethynylheteroarenes. Bergman cyclization, schreinerpascal cyclization, myerssaito cyclization, schmittel cyclization, garratt braverman cyclization, dehydrodielsalder reactions, cycloaromatization. Intramolecular pericyclic reactions of acetylene derivatives leading to dehydroaromatic and related species volume. This dissertation describes research in organic chemistry including quantum mechanical investigations of dielsalder reaction, 1,3dipolar cycloadditions and bioorthogonal reactions, and dynamic investigations of several cope rearrangements and the bergman cyclization. We specialise in professionalquality tools and accessories for the home and garden. Department of chemistry, university of wisconsineau claire, p. We investigate the thermally induced cyclization of 1,2bis2phenylethynylbenzene on au111 using scanning tunneling microscopy and computer simulations. This preference is explained by stereoelectronic effects where formation of the fivemembered ring is favored because of better orbital overlap. Taking into account the estimated cyclization barrier of 42 kcalmol, the fulvene diradical.
Bergman cyclization in polymer chemistry and material science bergman cyclization in polymer chemistry and material science xiao, yuli. Request pdf an acyclic enediyne anticancer compound attributed to a bergman cyclization at physiological temperature enediyne cytotoxic drugs have attracted much attention because of their. The dehydrogenation reactions may involve isomerization and cyclization as well as the formation of olefins and unsaturated compounds generally. The bergman cyclization reaction generates a diradical, which then becomes benzene after the addition of two hydrogen atoms or h dot. Very recently, we also reported a novel strategy toward indolo3,2acarbazoles, and the key transformations involved a biomimetic transaminationaromatic cyclization sequence to deliver 9methoxycarbonyl indolo3,2acarbazole derivatives. This image for the bergman cyclization needs to be corrected. Enediyne, photochemistry, photomedicine, cyclopropenone, diazoketone. Kc russell publications northern kentucky university. Relative reactivity of benzothiophenefused enediynes in. Bergman cyclization in polymer chemistry and material science. Best example of nazarov cyclization for csir net chemical science gate chemistry duration.
Request pdf bergman cyclization in polymer chemistry and material science bergman cyclization of enediynes, regarded as a promising. Results both in one and several complex variables are obtained. More than 2,600 structures illustrate key concepts throughout the book. The activation energies of these compounds toward bergman cyclization, including the remarkable reactivity of 3, are described. Bartonmccombie reaction barton desoxygenation baylishillman reaction. Very recently, we also reported a novel strategy toward indolo3,2acarbazoles 8, and the key transformations involved a biomimetic transaminationaromatic cyclization sequence to deliver 9methoxycarbonyl indolo3,2acarbazole derivatives. Most cyclizations have a high activation energy barrier and therefore temperatures around 200 c are needed for the cycloaromatization. The bergman cyclization allows the construction of substituted arenes through the thermal or photochemical cycloaromatization of enediynes in the presence of. Our aim is to produce intelligent and practical products which help get gardening and diy jobs done in half the time. The results of deuterium labeling experiments are consistent with a mechanism that proceeds via a 6 electrocyclization to form an 4isobenzene adduct followed by a metalmediated 1,5hydride shift. Thermal bergman cyclization of tetraalkynylporphyrins affords the dialkynylpicenoporphyrins in trace to 30 % yields, but no fully cyclized bispicenoporphyrin. Very recently, we also reported a novel strategy toward indolo3,2acarbazoles, and the key transformations involved a biomimetic transaminationaromatic cyclization sequence to deliver 9methoxycarbonyl indolo3,2.
Pdf reversible bergman cyclization by atomic manipulation. It is the most famous and wellstudied member of the general class of. The design and activation of enediyne prodrugs that cleave dna upon bergman cyclization 1 remains a formidable synthetic challenge. The bergman cyclization is one of the most fascinating rearrangemen ts in c hemistry, with impor tan t implications in organic syn thesis and pharmacology. Pdf file for the applications of gatterman koch carbonylation. While at wisconsin he was awarded a national institutes of health predoctoral fellowship. Acyl acridines were synthesized through rhodiumiii. Department of chemistry,university of georgia, athens, ga 30602, usa. It is the most famous and wellstudied member of the general class of cycloaromatization reactions. We study the bergman kernel on a domain having smooth boundary with several connected components, and relate it to the bergman kernel of simpler domains having only some of these boundary components. Oct 01, 2019 cyclization plural cyclizations the process of cyclizing, of becoming or causing to become aromatic. Facile synthesis of indolo3,2acarbazoles via pdcatalyzed. Several methods for the construction of the indolo3,2acarbazole skeleton were developed by bergman, cachet, and zhiping li. You can use them to display text, links, images, html, or a combination of these.
Harvardsadvancedorganicchemistry2003 identifierark ark. Jul 18, 2017 this is a text widget, which allows you to add text or html to your sidebar. All structured data from the file and property namespaces is available under the creative commons cc0 license. Synthesis of carbazoles and dibenzofurans via cross.
The last chapter covers macrolactonization, vicinal tricarbonal, and bergman enediyne reactions, which are of particular interest today. Mechanism of the bergman cyclization organic chemistry portal. Like our earlier work on nsubstituted enediyne and also kerwins work on azaenediynes, 14 we decided to incorporate a nitrogen atom at the terminal ethylenic carbon and to constrain the moiety in a ninemembered cyclic network and to study its reactivity. Such high endothermicity is not surprising because, unlike in the bergman cyclization, the product is not stabilized by aromaticity. Single and twophoton triggering of bergman cyclization volume. To find promising analogues of naturally occurring enediyne antibiotics with a sufficient reactivity in the bergman cyclization and moderately stable under isolation and storage, a scale of relative enediynes reactivity was created on the basis of calculated free activation energies for the bergman cyclization within 12 known and new benozothiophene, benzene, and cinnoline annulated 9 and 10.
Request pdf recent advances of the bergman cyclization in polymer science the bergman cyclization has strongly impacted on a number. Russell photochemical and thermal bergman cyclization of a pyrimidineenediynol and enediynone. Relative reactivity of benzothiophenefused enediynes in the. Deuterium labeling experiments led to a mechanistic proposal involving 6complexation of ruthenium to the triene followed by disrotatory electrocyclic ring closure. Observation and characterization of an 6triene ruthenium complex were accomplished. Boundary decomposition of the bergman kernel steven g. Reversible bergman cyclization by atomic manipulation. Bergman cyclization synthetic application of the bergman cyclization is rare. Nov 01, 2011 bergman cyclization of enediynes, regarded as a promising strategy for anticancer drugs, now finds its own niche in the area of polymer chemistry and material science. The person who associated a work with this deed has dedicated the work to the public domain by waiving all of their rights to the work worldwide under law, including all related and neighboring rights, to the extent allowed by law. This page was last edited on 23 november 2016, at 07.
H aminations of aldimines with anthranils followed by intramolecular cyclization. Rutheniummediated cycloaromatization of tripi systems. Bergman was born in chicago, illinois, on may 23, 1942. The highly reactive aromatic diradicals generated from bergman cyclization can undergo polymerization acting as either monomers or initiators of other vinyl monomers.
Benzannulated cyclic enediynes produced by the photodecomposition of enediyne precursor containing 2diazo1,3diketones possess enolized. Like our earlier work on nsubstituted enediyne and also kerwins work on azaenediynes, 14 we decided to incorporate a nitrogen atom at the terminal ethylenic carbon and to constrain the moiety in a ninemembered cyclic network and to study. Photochemical bergman cyclization and related reactions arene. Cyclization definition and meaning collins english. Basak reports a real interesting use of this reaction to create polycyclic aromatics. This file is made available under the creative commons cc0 1. Cyclization of sterically hindered enediynes is known to proceed via two competing mechanisms in solution. Grosse, dehydrogenation of hydrocarbons, us patent 2148129, page 1. Bergman 1942 is a professor at the university of california, berkeley.
The cyclization is induced thermally or photochemically. Noncovalent dimerization after enediyne cyclization on au111. Bergman cyclization of enediynes, regarded as a promising strategy for anticancer drugs, now finds its own niche in the area of polymer chemistry and material science. The bergman cyclization is an endothermic reaction and the formed 1,4. Harvards advanced organic chemistry internet archive. Bergman an invitation to general algebra and universal constructions april 2, 2015 springer. An ab initio exploration of the bergman cyclization iopenshell. The generation of reactive enediyne was also achieved with nir light by non resonant twophoton excitation. The enediyne antitumor antibiotics utilize complex molecular architectures to control delivery and activation of enediyne warheads, leading to their potent cytotoxicity. Grosse, dehydrogenation of hydrocarbons, us patent 2148129 1, page 1.
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