Adducts of Tricyclo[4.1.0.0<Superscript>2,7</Superscript>]heptane hydrocarbons with methane- and Halomethanesulfonyl Thiocyanates and their transformations in the presence of bases (nucleophiles)

1-R-Tricyclo[4.1.0.0^2,7]heptanes (R = H, Me, Ph) take up methane- and halomethanesulfonyl thiocyanates XCH₂SO₂SCN (X = H, Cl, Br) at the central C¹–C⁷ bond in benzene at 20°C with high anti-selectivity to give bicyclo[3.1.1]heptane derivatives with the 7-endo-oriented sulfonyl group and the thiocyanato group in the geminal position with respect to the R substituent. The syn-adducts lose HSCN molecule by the action of potassium tert-butoxide in THF at 0°C or on heating in boiling aqueous dioxane containing NaOH with formation of 1-(X-methylsulfonyl)tricyclo[4.1.0.0^2,7]heptanes. Under analogous conditions the anti-adducts (X = Me) are converted into 1,2-bis(7-syn-methylsulfonyl-6-endo-R-bicyclo[3.1.1]hept-6-exo-yl)disulfanes. The anti-adduct derived from unsubstituted tricyclo[4.1.0.0^2,7]heptane and MeSO₂SCN reacted with methyllithium or phenylmagnesium bromide to produce 7-anti-methyl(phenyl)sulfanyl-6-endo-methylsulfonylbicyclo-[3.1.1]heptanes which were also obtained by photochemical addition of MeSO₂SMe(or Ph) to tricyclo-[4.1.0.0^2,7]heptane. Geometric parameters of radical intermediates in the sulfonylation of 1-R-tricyclo-[4.1.0.0^2,7]heptanes were optimized ab initio using 6-31G basis set.     

Stereoselectivity of halomethoxylation of 1-phenyltricyclo-[4.1.0.0<Superscript>2,7</Superscript>]heptane and methyl 7-phenyltricyclo[4.1.0.0<Superscript>2,7</Superscript>]-heptane-1-carboxylate

The stereoselectivity of halomethoxylation of 1-phenyltricyclo[4.1.0.0^2,7]heptane and methyl 7-phenyltricyclo[4.1.0.0^2,7]heptane-1-carboxylate at the central bicyclobutane C¹-C⁷ bond by the action of N-chloro-, N-bromo-, and N-iodosuccinimides in methanol depends on the halogen nature. Conjugate chlorination and bromination are characterized by pronounced anti-stereoselectivity; the contribution of syn-addition slightly increases in going from the monosubstituted tricycloheptane substrate to disubstituted. Iodomethoxylation of the latter is clearly syn-stereoselective.     

Chemo-, regio-, and stereoselectivity in acid-catalyzed hydromethoxylation of tricyclo[4.1.0.0<Superscript>2,7</Superscript>]hept-1-yl and 7-methyltricyclo[4.1.0.0<Superscript>2,7</Superscript>]hept-1-yl phenyl sulfones

Hydromethoxylation of tricyclo[4.1.0.0^2,7]hept-1-yl and 7-methyltricyclo[4.1.0.0^2,7]hept-1-yl phenyl sulfones with methanol at 20°C in the presence of a catalytic amount of perchloric acid is initiated by the endo attack of proton at the C¹ atom, and the subsequent cleavage of the side C¹–C² bond leads to formation of mixtures of diastereoisomeric exo-7-phenylsulfonyl-2-methoxybicyclo[4.1.0]heptanes, the endo-2 isomer prevailing. Probable factors responsible for the observed chemo-, regio-, and stereoselectivity of the addition are discussed.     

Synthesis of 7-sulfonyl-substituted norpinan-6-ones and -thiones from 1-bromotricyclo[4.1.0.0<Superscript>2,7</Superscript>]heptane

1-Bromotricyclo[4.1.0.0^2,7]heptane reacted with benzene- and methanesulfonyl thiocyanates in benzene at 20°C via anti addition to the central C¹–C⁷ bicyclobutane bond with formation of 6-endo-bromo-6-exo-thiocyanato-7-syn-(R-sulfonyl)bicyclo[3.1.1]heptanes. Treatment of the benzenesulfonyl thiocyanate adduct with potassium tert-butoxide in THF at 20°C gave 7-endo-(benzenesulfonyl)norpinan-6-one, whereas the reaction with 1,8-diazabicyclo[5.4.0]undec-7-ene in methylene chloride afforded 7-exo-(benzenesulfonyl)-norpinane-6-thione which was converted into 7-exo-(benzenesulfonyl)norpinan-6-one by alkaline hydrolysis.     

First synthesis of nitro-substituted bicyclo[1.1.0]butane derivatives and new method for generation of tricyclo[4.1.0.0<Superscript>2,7</Superscript>]hept-1(7)-ene

Successive treatment of 1-phenylsulfonyltricyclo[4.1.0.0^2,7]heptane with butyllithium and ethyl nitrate leads to the formation of 7-nitro-7′-phenylsulfonyl-1,1′-bi(tricyclo[4.1.0.0^2,7]heptane) through intermediate tricyclo[4.1.0.0^2,7]hept-1(7)-ene which is generated by 1,2-elimination of benzenesulfinic acid from the initial compound. Analogous treatment of 1-phenyltricyclo[4.1.0.0^2,7]heptane gives 1-nitro-7-phenyltricyclo[4.1.0.0^2,7]heptane.     

Regio- and stereoselective addition of methane- and bromomethanesulfonyl bromides to 1-phenylthiotricyclo[4.1.0.0<Superscript>2,7</Superscript>]heptane

1-Phenylthiotricyclo[4.1.0.0^2,7]heptane reacted with MeSO₂Br and BrCH₂SO₂Br directly at mixing at 20°C in CH₂Cl₂ along a ionic (electrophilic with respect to bromine) mechanism affording a product of an antistereoselective addition to the central bicyclobutane C¹–C⁷ bond of the norpinane structure. The reaction product contains the exo-oriented sulfonyl group in the geminal position to the SPh substituent. The structure of the adduct with MeSO₂Br in a single crystal was determined by XRD analysis.     

Stereochemistry of conjugate halogenation of 1-phenyltricyclo[4.1.0.0<Superscript>2,7</Superscript>]heptane

1-Phenyltricyclo[4.1.0.0^2,7]heptane reacts with N-bromo- and N-chlorosuccinimides in the presence of external nucleophiles providing products of a conjugate (electrophilic with respect to halogen) addition across the central bond C¹-C⁷ of the bicyclo[3.1. 1]heptane structure with a pronounces endo, anti-stereoselectivity. In similar reactions with N-iodosuccinimide the products obtained originated mainly from endo, syn-addition across the C¹-C⁷ bond. The reasons for differences in the selectivity of the conjugate halogenation are discussed applying the data of the quantum-chemical calculation in the basis MP2/STO 3G of the electronic and spatial structure of the reaction intermediates, norpinanyl cations of benzyl type.Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 11, 2004, pp. 1647–1655.Original Russian Text Copyright © 2004 by Vasin, Semenov, Razin.     

Stereoselective synthesis of substituted bicyclo[3.1.1]heptanes: II.* Synthesis of all diastereoisomers of 7-methyl-and 7-phenylbicyclo[3.1.1]hept-6-yl phenyl sulfones from tricyclo[4.1.0.02,7]heptane precursors

All four possible diastereoisomers of 7-methyl-and 7-phenylbicyclo[3.1.1]hept-6-yl phenyl sulfones were intentionally synthesized from tricyclo[4.1.0.0^2,7]heptane and 1-phenyltricyclo[4.1.0.0^2,7]heptane, respectively. The key stage in the synthesis was regio-and stereoselective cleavage of the central bicyclobutane C¹-C⁷ bond in the tricycloheptane precursors by the action of radical, nucleophilic, and electrophilic reagents. The NMR spectra of the diastereoisomers were compared.     

Hydrogenolysis of 7-phenyltricyclo[4.1.0.0<Superscript>2,7</Superscript>]heptan-1-carboxylic acid. Synthesis of ketones with tricyclo[4.4.0.0<Superscript>2,7</Superscript>]decane and tricyclo[5.4.0.0<Superscript>2,8</Superscript>]undecane skeletons

Hydrogenation of 7-phenyltricyclo[4.1.0.0^2,7]heptane-1-carboxylic acid over Raney nickel occurred in the syn-stereoselective fashion to give anti-7-phenylbicyclo[3.1.1]heptane-exo-6-carboxylic acid. The latter was used to synthesize 4,5-benzotricyclo[4.4.0.0^2,7]dec-4-en-3-one and two isomeric higher homologs, 5,6-benzotricyclo[5.4.0.0^2,8]undec-5-en-3-and-4-ones.     

Regio- and stereoselectivity in halomethoxylation of 7-phenyl-1-phenylsulfonyltricyclo[4.1.0.02,7]heptane

The reaction of 7-phenyl-1-phenylsulfonyltricyclo[4.1.0.0^2,7]heptane with N-halo(chloro, bromo, iodo)succinimide in methanol led to the formation of a single product of conjugate syn-addition to the central C¹–C⁷ bond of the norpinane structure with a halogen atom in the geminal position to the sulfonyl substituent. The stereochemical result of the addition originates from the features of the reaction intermediate structure, a norpinanyl cation of a benzyl type where the reaction site is shielded from the nucleophile attack from the anti-direction by the sulfonyl group whose oxygen atom is approached to the reaction site to a distance of ～1.45 Å according to the nonempirical calculations by the 6-31G method; this distance is nearly by half less than the sum of van der Waals radii of C?O.     

Reaction products of methyl tricyclo[4.1.0.02,7]heptane-1-carboxylate and tricyclo[4.1.0.02,7]hept-1-yl phenyl sulfone with dinitrogen tetraoxide

The reaction of methyl tricyclo[4.1.0.0^2,7]hepatne-1-carboxylate with dinitrogen tetraoxide in diethyl ether at ?10 to 0°C, followed by treatment of the reaction mixture with methanol, gave approximately equal amounts of methyl exo,syn-6,7-dinitro-and exo-6-hydroxy-syn-7-nitrobicyclo[3.1.1]heptane-endo-6-carboxylates. Tricyclo[4.1.0.0^2,7]hept-1-yl phenyl sulfone reacted with dinitrogen tetraoxide under analogous conditions to produce a mixture of diastereoisomeric exo,syn-and endo,syn-6,7-dinitro-6-phenylsulfonylbicyclo-[3.1.1]heptanes and 6,6-dimethoxy-endo-7-nitrobicyclo[3.1.1]heptane at a ratio of 4.5:2:1. Probable factors responsible for the different stereoselectivities in the addition of N₂O₄ at the central C¹-C⁷ bond of the initial tricycloheptane compounds were discussed. The structural parameters of the dinitro ester and related dinitro sulfone were compared on the basis of the X-ray diffraction data.     

Conjugate Iodination of 1-Methyltricyclo[4.1.0.02,7]heptane

Reactions of 1-methyltricyclo[4.1.0.0^2,7]heptane with N-iodosuccinimide in the presence of external nucleophiles result in products of conjugate endo,syn-addition across the central C¹C⁷ bond of the norpinane structure. Regio- and stereoselectivity of reactions is discussed.     

Regio-and stereoselectivity in the halogenation of methyl tricyclo[4.1.0.02,7]heptane-1-carboxylate

Conjugate halogenation of methyl tricyclo[4.1.0.0^2,7]heptane-1-carboxylate by the action of N-iodoand N-bromosuccinimides in the presence of halide ions occurs exclusively at the central bicyclobutane C¹–C⁷ bond via electrophilic attack on the C¹ atom, leading to endo,syn-adducts of the norpinane series. Reactions of the title compound with iodine, dibromotetrachloroethane, and (dichloro-λ³-iodanyl)benzene give not only the corresponding 6,7-endo,syn-dihalonorpinane but also its epimer at C⁶, indicating radical mechanism of the halogenation. The regio-and stereoselectivity observed in these ionic and radical reactions are discussed in terms of the results of nonempirical MP2/STO-3G calculations of appropriate cationic and radical intermediates.     

Nitrochlorination of methyl tricyclo[4.1.0.02,7]heptane-1-carboxylate and phenyl tricyclo[4.1.0.02,7]hept-1-yl sulfone

Treatment of methyl tricyclo[4.1.0.0^2,7]heptane-1-carboxylate and phenyl tricyclo[4.1.0.0^2,7]hept-1-yl sulfone with a ～1:8 mixture of N₂O₄ and NOCl in diethyl ether at ?5 to 0°C gave products of formal anti-addition of NO₂Cl at the central C¹-C⁷ bond. In the reaction with phenyl tricyclo[4.1.0.0^2,7]hept-1-yl sulfone nitryl chloride acts as an effective chlorinating agent; as a result, a mixture of diastereoisomeric syn- and anti-6,7-dichlorobicyclo[3.1.1]hept-6-yl phenyl sulfones at a ratio of 7.5:1 is formed.     

Synthesis and isomerization of epoxides derived from 7-phenylsulfonyl-and 7-methylsulfonyl-6-methylidenebicyclo[3.1.1]heptanes

Oxidation of exo-7-phenylsulfonyl-and exo-7-methylsulfonyl-6-methylidenebicyclo[3.1.1]heptanes with m-chloroperoxybenzoic acid gave the corresponding epoxy derivatives, anti-7-phenylsulfonyl-and anti-7-methylsulfonyl-endo-2′-oxaspiro[bicyclo[3.1.1]heptane-6,2′-cyclopropanes]. Treatment of the phenylsulfonyl-substituted epoxide with potassium tert-butoxide in THF led to the 1,3-cyclization product, 7-phenylsulfonyltricyclo[4.1.0.0^2,7]hept-1-ylmethanol. anti-7-Methylsulfonyl-endo-2′-oxaspiro[bicyclo[3.1.1]heptane-6,2′-cyclopropane] under analogous conditions underwent 1,6-cyclization, being converted into 6-hydroxy-3λ⁶-thiatricyclo[4.4.0.0^2,7]decane 3,3-dioxide.     

<Emphasis Type="Italic">O</Emphasis>- and <Emphasis Type="Italic">N</Emphasis>-Alkylation of <Emphasis Type="Italic">N</Emphasis>-halosuccinimides in ionic reactions with 1-phenyltricyclo [4.1.0.0<Superscript>2,7</Superscript>]heptane

N-Bromo and N-chlorosuccinimides add to 1-phenyltricyclo[4.1.0.0^2,7]heptane in CH₂Cl₂ with cleavage of the C(1)-C(7) bond to give isomeric 1 : 1 Markownikoff-type endo, anti-adducts of the norpinane structure in a ∼3 :7 ratio corresponding to N and O alkylation of succinimide.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No.2, pp. 457–460, February, 2005     

13C-NMR-Spektren von Tetracyclo[4.1.0.02,4.03,5]heptanen,Tetracyclo[5.1.0.02,4.03,5]octanen und Tricyclo[4.1.0.02,7]hept-3-enen. Ungewöhnliche δ- und γ-Substituenteneffekte

Carbon-13 NMR spectroscopic data of eleven tetracyclo[4.1.0.0^2,4.0^3,5]heptanes, two tetracyclo-[5.1.0.0^2,4.0^3,5]octanes and twelve tricyclo[4.1.0.0^2,7]hept-3-enes are reported. In the tetracycloheptanes, halogens located at the 7-position cause large δ substituent effects. endo-Halogens shift the C-4 signal to lower field by about 6 ppm, while exo-haolgens produce upfield shifts of the C-3 signal, which are dependent on the nature of the halogen and reach a maximum of 9.1 ppm in the case of fluorine. An orbital model is proposed to explain the δ upfield shifts. The compounds containing fluorine reveal a connection between the δ substituent effects and the corresponding ¹³C? ¹⁹F coupling constants. Substituents in the 5 position of tricycloheptenes are γ-substituents of C-1, C-3 and C-7 and produce downfield shifts of the absorptions of these nuclei. Their dependence on the nature of the substituent follows approximately those in 1-substituted adamentanes; in the case of C-7, however, their magnitude by far exceeds the adamantane values, bromine (15.5 ppm) being most effective.     

Functionalization of one or two methyl groups in the [Cp*<Subscript>2</Subscript>RuBr]<Superscript>+</Superscript>Br<Superscript>−</Superscript> complex in the reaction with bromine

The reaction of [Cp*₂RuBr]⁺Br⁻ with bromine in CH₂Cl₂ (CD₂Cl₂) in an inert atmosphere at room temperature produces the complexes [Cp*Ru(Br)C₅Me₄CH₂Br]⁺Br₃ ⁻ (syn conformer), [Cp*Ru(Br)C₅Me₃(CH₂Br)₂]⁺ (syn and anti conformers), and [Ru(Br)(C₅Me₄CH₂Br)₂]⁺ (syn conformer). All complexes were characterized by ¹H and ¹³C NMR spectroscopy; the former complex, by elemental analysis. These complexes were also prepared by the reaction of [Cp*RuC₅Me₄CH₂]⁺BF₄ ⁻ with bromine in CH₂Cl₂. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2712–2718, December, 2005.     

An Efficient <Emphasis Type="Italic">Mannich</Emphasis>-Type One-Pot Synthesis of 3,5,7,11-Tetraazatricyclo [7.3.1.0<Superscript>2,7</Superscript>]tridec-2-ene Derivatives Starting from Functionalized 1,4-Dihydropyridines

Summary. 3,5,7,11-Tetraazatricyclo[7.3.1.0^2,7]tridec-2-ene derivatives were prepared in one-pot manner from N-methylmorpholinium 6-amino-3,5-dicyano-4-spiro(1′-cycloalkane)-1,4-dihydropyridine-2-thiolates, primary amines, and formaldehyde in 70–88% yields. The structure of 5,11-dibenzyl-13-spiro(1′-cyclopentane)-8-thioxo-3,5,7,11-tetraazatricyclo[7.3.1.0^2,7]tridec-2-ene-1,9-dicarbonitrile was determined by X-ray diffraction analysis.     

Reactions of [Cp*Ru(H<Subscript>2</Subscript>O)(NBD)]<Superscript>+</Superscript> with diynes

Abstract  Formal [2 + 2 + 2] addition reaction of [Cp*Ru(H₂O)(NBD)][BF₄] (NBD = norbornadiene) with 4,4′-Diethynylbiphenyl generates [C₉H₉-η⁶-C₆H₄(RuCp*)–C₆H₄(RuCp*)-η⁶-C₉H₉][BF₄]₂. The reaction of [Cp*Ru(H₂O)(NBD)][BF₄] with 1,4-diphenylbutadiyne generates the unusual [2 + 2 + 2] additional organic compound Ph–C≡C–C₉H₈–Ph in addition to the organometallic compound [Cp*Ru(η⁶-C₆H₅–C≡C–C≡C–Ph)][BF₄]. [C₉H₉-η⁶-C₆H₄(RuCp*)–C₆H₄(RuCp*)-η⁶-C₉H₉][BPh₄]₂ is generated after the reaction of compound [C₉H₉-η⁶-C₆H₄(RuCp*)–C₆H₄(RuCp*)-η⁶-C₉H₉][BF₄]₂ with Na[BPh₄]. The structure of this compound was confirmed by X-ray diffraction. A possible approach to form Ph–C≡C–C₉H₈–Ph and [Cp*Ru(η⁶-C₆H₅–C≡C–C≡C–Ph)][BF₄] is suggested. Graphical Abstract  Formal [2 + 2 + 2] addition reaction of [Cp*Ru(H₂O)(NBD)]BF₄ (NBD = norbornadiene) with 4,4′-Diethynylbiphenyl generates [C₉H₉-η⁶-C₆H₄(RuCp*)–C₆H₄(RuCp*)-η⁶-C₉H₉][BF₄]₂. The reaction of [Cp*Ru(H₂O)(NBD)][BF₄] with 1,4-diphenylbutadiyne simply generates unusual [2 + 2 + 2] additional organic compound Ph–C≡C–C₉H₈–Ph in addition to the organometallic compound [Cp*Ru(η⁶-C₆H₅–C≡C–C≡C–Ph)][BF₄]. [C₉H₉-η⁶-C₆H₄(RuCp*)–C₆H₄(RuCp*)-η⁶-C₉H₉][BPh₄]₂ is generated after the reaction of compound [C₉H₉-η⁶-C₆H₄(RuCp*)–C₆H₄(RuCp*)-η⁶-C₉H₉][BF₄]₂ with Na[BPh₄]. The structure of this compound was confirmed by X-ray diffraction. And the possible approach to form Ph–C≡C–C₉H₈–Ph and [Cp*Ru(η⁶-C₆H₅–C≡C–C≡C–Ph)][BF₄] was suggested. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.