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Intramolecular reaction
About: Intramolecular reaction is a research topic. Over the lifetime, 5015 publications have been published within this topic receiving 138213 citations.
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110 citations
TL;DR: In this paper, the reaction of NUC-allylpalladium complexes with carbon nucleophiles is a well-established reaction both stoichiometric and catalytic reactions are possible.
Abstract: Various transformations of allylic esters and ethers via ir—allylic complexes catalyzed by palladium—phosphine complexes have been studied Intramolecular reaction of a nucleophile offers a good synthetic method for five—membered ring ketones Also nucleophiles reacted easily with ct—acetoxy—,y—unsaturated nitriles and 1,3—diene monoepoxides It was found that the Carroll rearrangement is catalyzed by palladium complexes under mild conditions Facile formation of conjugated dienes and terminal olefins from allylic esters and ethers has been studied INTRODUCTION Palladium complexes catalyze numerous reactions (Refl) One important and unique group of reactions catalyzed by palladium complexes is the transformation of various allylic compounds Especially allylic ethers and esters undergo various reactions smoothly in the presence of palladium—phosphine complexes as a catalyst In the reaction of these allylic compounds, the first step is the oxidative addition of allylic compounds to Pd° species to form ir—allylpalladium complexes, which then undergo several transformations In this paper, several transformations of various allylic compounds catalyzed by palladium complexes discovered in our laboratory are presented REACTIONS OF NUCLEOPHILES The reaction of ¶-allylpalladium complexes with nucleophiles is a wellestablished reaction Both stoichiometric and catalytic reactions are possible (Ref2) Especially the reaction with carbon nucleophiles offers a good method for carbon—carbon bond formation We have studied further synthetic applications of reactions of allylic compounds via ir-allylpalladium complexes We have carried out studies aimed at preparing fiveand six-membered cyclic ketones by the palladium—catalyzed intramolecular reaction of active methylene with allyl phenyl ether moiety We have synthesized methyl (E)-3-oxo-8phenoxy-6-octenoate (1) by the reaction of the dianion of methyl acetoacetate with (E)-l-chloro-4-pfienoxy-2-butene (77% yield), and carried out its cyclization using 5-10 mol% of Pd(OAc)2-piosphine or phosphite as a catalyst in various solvents without using a base (Ref3) 0 CO2Me OPh 1 2Me eCO2Me + Pd(OAc)2 PPh3 2 —Pd(OAc)2 P T'°JCO2Me
110 citations
TL;DR: A pentacyclic compound was synthesized as an important intermediate of antitumor antibiotic dynemicins as discussed by the authors, using the Heck reaction using catalytic Pd reagent, and an unusual spiro ring compound was found to be produced via intramolecular conjugate addition.
109 citations
TL;DR: Rhodium(I) chiral diphosphine complexes efficiently and rapidly catalyze the intramolecular hydrosilation of silyl ethers derived from allylic alcohols.
Abstract: Rhodium(I) chiral diphosphine complexes efficiently and rapidly catalyze the intramolecular hydrosilation of silyl ethers derived from allylic alcohols. The efficiency and rates of intramolecular hydrosilations were determined for a variety of silyl and olefin substituents. The catalysts were found to tolerate a widevariety of silyl substituents, although terminal alkyl olefin substituents were found to retard catalysis. Terminal aryl olefinsubstituents were found to be hydrosilated efficiently and at reasonable rates
109 citations
TL;DR: Through an intramolecular C-C bond formation of diarylamines by the S(RN)1 mechanism, carbazoles were achieved and substituted 9H-carbazoles, benzocarbazoles and even 3,3'-bi(9H- carbazole) were obtained by a double S( RN)1 reaction with benzidine.
Abstract: The synthesis of a series of substituted 9H-carbazoles by the photostimulated SRN1 substitution reaction with diarylamines as starting substrate was performed. The diarylamines were obtained by two approaches, the Pd-catalyzed reactions (Buchwald−Hartwig) or Cu-catalyzed reactions of 2-haloanilines with aryl halides, or 2-bromoiodobenzene with anilines, with moderate to very good isolated yields (45−89%). Through an intramolecular C−C bond formation of diarylamines by the SRN1 mechanism, carbazoles were achieved. These reactions proceeded synthetically in very good to excellent yields (81−99%) in liquid ammonia and DMSO. The reaction of N-(2-bromophenyl)-2-phenylbenzenamine gave 1-phenyl-9H-carbazole (38%) and the isomer 9H-tribenz[b,d,f]azepine (58%). By using this methodology, 9H-carbazoles, substituted 9H-carbazoles, benzocarbazoles, and even 3,3′-bi(9H-carbazole) were obtained by a double SRN1 reaction with benzidine.
109 citations