An efficient route to bicycle[3.3.1] intermediate employing organocatalytic Michael/Aldol biannulation: a formal synthesis of (+)-Huperzine A

The key intermediate for the synthesis of (+)-Huperzine A, bicycle[3.3.1]nona-2,6-dien-9-one core, was prepared by Michael–Aldol annulation of β-ketoesters and methacrolein catalyzed by α,α-diarylprolinol silyl ether in highest 87 % ee and with up to 80 % ee in the gram-scale procedure.     

Reactions of α,β-unsaturated ketones of the bicyclo[3.3.1]nonane series with nitro alkanes

Reaction of bicyclo[3.3.1]nona-3,7-diene-2,6-dione with nitroform in boiling methanol occurs with involvement of the solvent and results in 2,6-dimethoxy-4,8-bis(trinitromethyl)-bicyclo[3.3.1]nona-2,6-diene, while the reaction in tert-butyl alcohol affords 4,8-bis(trinitromethyl)bicyclo[3.3.1]nona-2,6-dione.     

Heterotricyclodecane XIV. 2-Oxa-6-aza-adamantan und Derivate

The synthesis of 2-oxa-6-aza-adamantane ( 21 ) and several of its derivatives ( 13–20 , 22 , 23 , 25–34 , 37 , and 38 ) was achieved starting from the 9-azabicyclo[3.3.1]nona-2,6- dienes 2 , and 3 , and 9-oxabicyclo[3.3.1]nona-2,6-diene ( 1 ).     

Stereospecific Synthesis of Endo-6-Aryl-2-Oxobicyclo [3.3.1]Nonanes

Two alternate synthetic routes to endo-6-aryl-2-oxobicyclo 3.3.1 nonan [3a-d] by sterespecific catalytic hydrogenetion of the easily accessible 6-arylbicyclo 3.3.1 nona-3,6-dien-2-ones [2a-d], and regioselective oomologation of endo-2-aryl-6-oxobicycle 3.2.1 octanes [4a-d] are described.     

2,4,6,8-Tetraazabarbaralanes: Models for tetraazasemibullvalenes

3,7-Diethoxy-1,5-dimethyl-2,4,6,8-tetraaza-bicyclo[3.3.1]nona-2,6-diene (7), readily obtained from the corresponding urea derivative, can be oxidized to afford 3,7-diethoxy-1,5- dimethyl-2,4,6,8-tetraazabarbaralane (9) whose crystal structure corresponds to a localized molecule. On heating, 9 gives rise to 2-ethoxy-4,6-dimethyl-pyrimidine.     

Efficient Synthesis of a New Family of 2,6-Disulfanyl-9-selenabicyclo[3.3.1]nonanes

The efficient synthesis of a new family of 2,6-disulfanyl-9-selenabicyclo[3.3.1]nonanes in high yields has been developed based on 9-selenabicyclo[3.3.1]nonane-2,6-dithiolate anion generated from bis-isothiouronium salt of 2,6-dibromo-9-selenabicyclo[3.3.1]nonane. The derivatives of 2,6-disulfanyl-9-selenabicyclo[3.3.1]nonane containing alkyl, allyl and benzyl moieties have been prepared in 90–99% yields by nucleophilic substitution of 9-selenabicyclo[3.3.1]nonane-2,6-dithiolate anion with alkyl, allyl and benzyl halides. The reaction of nucleophilic addition of 9-selenabicyclo[3.3.1]nonane-2,6-dithiolate anion to alkyl propiolates afforded 2,6-di(vinylsulfanyl)-9-selenabicyclo[3.3.1]nonanes. The conditions for regio- and stereoselective addition of 9-selenabicyclo[3.3.1]nonane-2,6-dithiolate anion to a triple bond of alkyl propiolates have been found. To date, not a single representative of 2,6-disulfanyl-9-selenabicyclo[3.3.1]nonanes has been described in the literature.     

C2-symmetric bicyclo[3.3.1]nonadiene as a chiral ligand for rhodium-catalyzed asymmetric arylation of N-(4-nitrobenzenesulfonyl)arylimines

[Reaction: see text] Asymmetric synthesis of diarylmethylamines with high enantioselectivity (95-99% ee) was realized by use of a new C2-symmetric diene ligand, (1R,5R)-2,6-diphenylbicyclo[3.3.1]nona-2,6-diene (Ph-bnd), for the rhodium-catalyzed asymmetric arylation of N-(4-nitrobenzenesulfonyl)arylimines with arylboroxines.     

Synthesis and Properties of Chiral Molecular Clefts Related to Tröger's Base

The chiral cavities present in 2,3:6,7-dibenzo-9-oxabicyclonona-2,6-diene, dibenzobicyclo[b,f][3.3.1]nona-5a, 6a-diene-6,12-dione, bicyclo[3.3.1]nonane and dibenzobicyclo[b,f],diazocines are reminiscent of Tröger's base, which has been widely used as a molecular cleft in supramolecular chemistry. The synthetic methodology to provide key derivatives for elaboration into new supramolecular structures, efficient resolution methods, the introduction of additional recognition groups and applications in supramolecular chemistry of these structurally related molecular clefts are reviewed.     

Palladium-catalyzed direct intramolecular double α-C–H arylation of 1,5-diketone: a strategy for synthesis of Tröger’s base analogues

9-Aryl-2,3:6,7-dibenzobicyclo[3.3.1]nona-2,6-diene-4,8-diones were straightforwardly prepared via a tandem reaction of easily available ortho-chloroacetophenone and ortho-chlorochalcone catalyzed by PdCl₂(PCy₃)₂.     

Synthese von 2-Thia-6-aza-adamantan und Derivaten

The synthesis of 2-thia-6-aza-adamantane ( 19 ) and several of its derivatives was achieved starting from 9-azabicyclo[3.3.1]nona-2,6-diene ( 9 ) which was prepared from cis, cis-cycloocta-1, 5-diene ( 1 ). Transannular addition of sulfur dichloride to its N-benzenesulfonyl and N-formyl derivatives 10 and 11 yielded the tricyclic dichlorides 12 and 13 , respectively; the 2-thia-6-aza-adamantanes 14–19 were synthesized from 13 .     

Cleft molecules as organocatalysts in an asymmetric hetero-Diels–Alder reaction

The synthesis and application of chiral carbocyclic cleft molecules derived from 2,3:6,7-dibenzobicyclo[3.3.1]nona-2,6-diene-4,8-dione in the hetero-Diels–Alder reaction of benzaldehydes and aminodiene 14 is presented. Catalysis by single hydrogen-bond activation gave up to 52% ee.     

Stereoselective synthesis of cyclic ethers via bromine assistedepoxide ring expansion

9-Oxabicyclo[6.1.O]non-4-ene reacts with bromine to give stereoselectively trans, trans-2,6-dibromo-9-oxabicyclo[3.3.1]nonane and trans, trans-2,5-dibromo-9-oxabicyclo[4.2.1]nonane.     

The synthesis and photochemistry of bicyclo[4.2.0]octa-2,4,7-trienes

Two new crystalline bicyclo[4.2.0]octa-2,4,7-trienes have been prepared by photodecarbonylation of the appropriate tricyclo[4.2.1.0^2,5]nona-3,7-dien-9-ones and their structures confirmed by ¹³C-n.m.r. The title compounds all undergo thermal ring opening to cyclooctatetraenes, but photolysis is substituent dependent.     

The diels-alder dimerisation of 2,3-dichlorocyclopentadienone and of 2,3,8,9-tetrachlorobicyclo[4.3.0]nona-2,4,8-trien-7-one

The Diels-Alder dimer of 2,3-dichlorocyclopentadienone, shown to be endo-4,5,7,8-tetrachlorotricyclo[5.2.1.0^2,6]deca-4,8-dien-3,10-dione 1, forms 2,3,8,9-tetrachlorobicyclo[4.3.0]nona-2,4,8-trien-7-one 3 on thermal extrusion of carbon monoxide. The trienone 3 itself dimerises at ca. 160°, with loss of hydrogen chloride, affording two stereoisomeric aromatic derivatives 8 and 9.     

Bicyclo[3.3.1]nonane and its derivatives—IV : Reactions of some carbonyl derivatives of bicyclo[3.3.1]nonane with diazomethane

The reaction of bicyclo[3.3.1]nonane-2,6-dione with diazomethane in situ does not lead to the homologous bicyclo[4.3.1]decane-2,7-dione, but mainly to tricyclo[4.4.0.0^2,9]decan-9-ol-5-one. The structure of the latter was confirmed by the proton NMR spectra measured with an addition of Eu(DPM)₃, A mixture of tricyclo[4,4.0.0^2,9]decan-9-ol-5-one and bicyclo[4.3.1]decane-2,7-dione results when solutions of diazomethane are used. The reaction of bicyclo[3.3.1]nonane-2,6-dione monoethyleneacetal with diazomethane in situ yields predominantly bicyclo[4.3.1]decane-2,7-dione. Under the same conditions bicyclo[3.3.1]nonan-2-one gives with diazomethane in situ only bicyclo[4.3.1]decan-2-one.     

Anomalous behaviour of an allyl alcohol in reaction with iron pentacarbonyl

[(6,7,8,9-η)-Bicyclo[3.2.2]nona-2,6,8-trien-4-ol]tricabonyliron (6) rearranges in the presence of Fe(CO)₅ to [(2,3,6,7-η)-bicyclo[3.2.2]nona-2,6,8-trien-4-one] tricarbonyliron (7); rather than [(6,7,8,9-η)-bicyclo-[3.2.2]nona-6,8-dien-2-one] tricarbonyliron (9), the product expected on the basis of known organoiron chemistry and previously proposed mechanisms. The starting material 6 is stable in the absence of Fe(CO)₅, which leads to the conclusion that some iron-containing species derived from fe(CO)₅ is responsible for bringing about rearrangement. Since the usual mechanism for iron carbonyl-induced rearrangement in olefins cannot be operating here, a mechanism involving an ion pair with [HFe(CO)₄]^- is suggested.     

Synthesis of 2,6-dimethyl-9-aryl-9-phosphabicyclo[3.3.1]nonanes: their application to asymmetric synthesis of chiral tetrahydroquinolines and relatives

Synthesis of 2,6-dimethyl-9-aryl-9-phosphabicyclo[3.3.1]nonanes from 1,5-cyclooctadiene and their application to asymmetric cyclization leading to chiral tetrahydroquinolines and relatives through palladium-catalyzed allylic alkylation are described.     

Five-membered 2,3-dioxo heterocycles: LXXXIX. Reaction of methyl 1-aryl-3-cinnamoyl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates with (E)-4-arylaminopent-3-en-2-ones. Crystalline and molecular structure of 9-acetyl-4-cinnamoyl-3-hydroxy-1-(4-methoxyphenyl)-8-methyl-7-phenyl-1,7-diazaspiro[4.4]nona-3,8-diene-2,6-dione

Methyl 1-aryl-3-cinnamoyl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates reacted with 4-benzylamino- and 4-arylaminopent-3-en-2-ones to give 1-aryl-7-benzyl- and 1,7-diaryl-9-acetyl-4-cinnamoyl-3-hydroxy-8-methyl-1,7-diazaspiro[4.4]nona-3,8-diene-2,6-diones. The crystalline and molecular structures of 9-acetyl-4-cinnamoyl-3-hydroxy-1-(4-methoxyphenyl)-8-methyl-7-phenyl-1,7-diazaspiro[4.4]nona-3,8-diene-2,6-dione were studied by X-ray analysis.     

C2-Symmetric bicyclo[3.3.1]nona-2,6-diene and bicyclo[3.3.2]deca-2,6-diene: new chiral diene ligands based on the 1,5-cyclooctadiene framework

As a new type of C₂-symmetric chiral diene ligands, which coordinate to a metal by their 1,5-cyclooctadiene framework, we prepared 2,6-disubstituted bicyclo[3.3.1]nona-2,6-diene (bnd*) and bicyclo[3.3.2]deca-2,6-diene (bdd*), and examined their catalytic activity and enantioselectivity for rhodium-catalyzed asymmetric 1,4-addition to α,β-unsaturated ketones and 1,2-addition to N-sulfonylimines. High enantioselectivity of the Ph-bnd* ligand was observed in the addition of phenylboroxine to N-tosylimine and N-4-nitrobenzenesulfonylimine of 4-chlorobenzaldehyde to give phenyl(4-chlorophenyl)methylamines in high enantiomeric excess (98–99% ee).     

Chemistry of 2-methylene-2,3-dihydro-3-furanones

[3+2]-Cycloaddition of 2-methoxycarbonylmethylene-5-phenyl-2,3-dihydro-3-furanone to acetone azine has been studied. This results in a monospirocycloadduct,viz., 9,9-dimethyl-6-methoxycarbonyl-2-phenyl-1-oxa-7,8-diazaspiro[4.4]nona-2,6-dien-4-one. Its structure has been confirmed by X-ray diffraction analysis.For the previous communication see Ref. 1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 306–308, February, 1994.