Formation of Azulene-Embedded Nanographene: Naphthalene to Azulene Rearrangement During the Scholl Reaction

Incorporation of a non-hexagonal ring into a nanographene framework can lead to new electronic properties. During the attempted synthesis of naphthalene-bridged double [6]helicene and heptagon-containing nanographene by the Scholl reaction, an unexpected azulene-embedded nanographene and its triflyloxylated product were obtained, as confirmed by X-ray crystallographic analysis and 2D NMR spectroscopy. A 5/7/7/5 ring-fused substructure containing two formal azulene units is formed, but only one of them shows an azulene-like electronic structure. The formation of this unique structure is explained by arenium ion mediated 1,2-phenyl migration and a naphthalene to azulene rearrangement reaction according to an in-silico study. This report represents the first experimental example of the thermodynamically unfavorable naphthalene to azulene rearrangement and may lead to new azulene-based molecular materials.     

Iodine(III)‐Catalyzed Rearrangements of Imides: A Versatile Route to α,α‐Dialkylated α‐Hydroxy Carboxylamides

A tertiary hydroxy group α to a carboxyl moiety comprises a key structural motif in many bioactive substances. With the herein presented metal‐free rearrangement of imides triggered by hypervalent λ³‐iodane, an easy and selective way to gain access to such a compound class, namely α,α‐disubstituted‐α‐hydroxy carboxylamides, was established. Their additional methylene bromide side chain constitutes a useful handle for rapid diversification, as demonstrated by a series of further functionalizations. Moreover, the in situ formation of an iodine(III) species under the reaction conditions was proven. Our findings clearly corroborate that hypervalent λ³‐benziodoxolones are involved in these organocatalytic reactions.     

A new reaction of vicinal sulfonyliminocarboxylates with phosphites

The reaction of alkyl trifluoro(organylsulfonylimino)propionates with phosphites occurs with NC transfer of the RSO₂ group and leads to sulfonyl-substituted trifluoroalanine derivatives. The novel rearrangement is interpreted as cheletropic 1,4-cycloaddition of the phosphite and subsequent 1,2-shift of the sulfonyl group in the intermediate cyclic phosphorane.     

Alkenylidenes in Organic Synthesis

Alkenylidenes R₂C?C: (= alkylidene carbenes) undergo regio- and stereoselective intramolecular C? H insertion reactions that are excellently suited for the synthesis of cyclopentenes. The 1, 2-shifts occurring with R?H and R?Ar are useful for the preparation of alkynes. Alkenylidenes are efficiently generated from carbonyl compounds by diazomethylation, from vinyl halides by α-elimination, from alkynyliodonium salts by addition of nucleophiles, and from alkynes by retro-1, 2-shifts. Specific applications of the various methods, particularly in the synthesis of natural products, are discussed.     

Structural properties and tractability results for linear synteny

The syntenic distance between two species is the minimum number of fusions, fissions, and translocations required to transform one genome into the other. The linear syntenic distance, a restricted form of this model, has been shown to be close to the syntenic distance. Both models are computationally difficult to compute and have resisted efficient approximation algorithms with non-trivial performance guarantees. In this paper, we prove that many useful properties of syntenic distance carry over to linear syntenic distance. We also give a reduction from the general linear synteny problem to the question of whether a given instance can be solved using the maximum possible number of translocations. Our main contribution is an algorithm exactly computing linear syntenic distance in nested instances of the problem. This is the first polynomial time algorithm exactly solving linear synteny for a non-trivial class of instances. It is based on a novel connection between the syntenic distance and a scheduling problem that has been studied in the operations research literature.     

Electron depleted bis(methylene)cyclobutenes: sulfinyl and sulfonyl substitution

Double [2,3] sigmatropic rearrangements of bis(propargyl sulfenates) to bis(allenic sulfoxides) and of bis(propargyl sulfinates) to bis(allenic sulfones) are shown to be a convenient and effective method for the preparation of conjugated diallene systems bearing two electron withdrawing trihalomethyl sulfoxide or sulfone substituents either on C-1 and C-6, or on C-3 and C-4. Such substituents are further shown to facilitate cyclization to bis(methylene)cyclobutenes, and to stabilize the latter. The electron withdrawing group substitution on the exocyclic methylene extremities proved more effective than similar substitution on the endocyclic double bond.     

Inter-ring η6⇌η5 haptotropic rearrangements of 18ē and 19ē (η5-pentamethylcyclopentadienyl)(η6-9-methylfluorenyl)iron complexes

New cationic complexes [(⁶-C₁₃H₁₀)Fe(⁵-Cp^*)]PF₆ and [(⁶-9-CH₃-C₁₃H₉)Fe(⁵-Cp^*)]PF₆ were obtained by the reaction of Cp^*Fe(CO)₂Br with fluorene and 9-methylfluorene, respectively. Deprotonation of these complexes byt-BuOK in THF affords zwitter-ionic compounds (⁶-C₁₃H₉)Fe(⁵-Cp^*) and (⁶-9-CH₃-C₁₃H₈)Fe(⁵-Cp^*) (A). WhenA is heated in nonane at 150 °C it undergoes ⁶⁵ inter-ring rearrangement with the formation of hexamethyldibenzoferrocene (B). The electrochemical behavior ofA andB was studied by cyclic voltammetry. One-electron reduction ofA andB to the corresponding radical anions induces inter-ring haptotropic rearrangementA ^.–B ^.–. The equilibrium in the 19 state is shifted to the ⁶-isomeric radical anionA ^.–, while in the 18 precursors, it shifts to the ⁵-isomerB.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 319–324, February, 1994.The authors are grateful to D. V. Zagorevskii (A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences) for recording and interpreting the mass spectra, and to A. A. Borisenko (Moscow State University) for recording the NMR spectra.This work was financially supported by the Russian Foundation for Basic Research (Grant 93-03-5209).     

Fast and reversible migrations of N,S-centered groups around the perimeter of cyclopropene and cycloheptatriene rings

The kinetics and mechanism of circumambulatory rearrangements of N-centered (NCS) and S-centered (SPh, SC₃Ph₃, SC(OEt)=S) groups in corresponding derivatives of 1,2,3-triphenylcyclopropene and cycloheptatriene were studied by dynamic¹H and¹³C NMR spectroscopy. Migrations of the isothiocyanate group occur by the dissociation-recombination mechanism with intermediate formation of a tight ionic pair. Migrations of the phenylthio group around the perimeter of cyclopropene and cycloheptatriene rings occur by the 1,2-shift mechanism. It was found that rearrangements of theO-ethyl dithiocarbonate group inS-(1,2,3-triphenylcyclopropen-3-yl)-O-ethyl dithiocarbonate occur by the 3,3-sigmatropic shift mechanism. The molecular and crystal structure ofO-ethylS-(1,2,3-triphenylcyclopropen-3-yl) dithiocarbonate was studied by X-ray analysis.     

Substituted and fused spiro[benzo-2-azepine-3,1′-cyclohexanes]

5-Methyl-4,5-dihydro-3H-spiro[benzo-2-azepine-3,1-cyclohexane] N-oxide was rear- ranged into 5-methyl-1-oxo-1,2,4,5-tetrahydro-3H-spiro[benzo-2-azepine-3,1-cyclohexane]. The latter was used for the synthesis of spiro{triazolo[3,4-a]- and-tetrazolo[5,1-a]benzo-2- azepinecyclohexanes}.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1647–1651, August, 2004.