Remote stereocontrol by the sulfinyl group: Mukaiyama aldol reactions of (S)-2-[2-(p-tolylsulfinyl)phenyl]acetaldehyde in the asymmetric synthesis of β-hydroxyacids and 1,3-diols

(S)-2-[2-(p-Tolylsulfinyl)phenyl]acetaldehyde reacts with different O-silylated ketenethioacetals in the presence of Yb(OTf)₃ yielding β-hydroxythioesters in high yields and diastereoselectivities. The obtained compounds were readily transformed into β-hydroxyacids and their corresponding diols. These Mukaiyama aldol reactions are a direct evidence of the ability of the sulfinyl group to control 1,5- and 1,6-asymmetric induction processes.     

Synthesis and properties of tricyclo[6.4.1.0]trideca-1,3(6),7,9,11-pentaene

A new cyclobutene-fused 1,6-methano[10]annulene was synthesized by pyrolysis of the sulfone and sulfinate adducts of 3,4-bis(methylene)-1,6-methano[10]annulene and its physical and chemical properties were disclosed.     

1,5-Diazabicyclo[3.1.0]hexanes and 1,6-diazabicyclo[4.1.0]heptanes: a new method for the synthesis,quantum-chemical calculations,and X-ray diffraction study

A new method was developed for the synthesis of 6-substituted 1,5-diazabicyclo[3.1.0]hexanes and 7-substituted 1,6-diazabicyclo[4.1.0]heptanes by condensation of N-monohalotrimethylene- and N-monohalotetramethylenediamines with carbonyl compounds in the presence of bases. X-ray diffraction studies and quantum-chemical B3LYP/6-31G* calculations demonstrated that the conformations of the resulting bicyclic systems are stabilized by stereoelectronic interactions. As a result, a boat conformation prevails in 1,5-diazabicyclo[3.1.0]hexanes, whereas the energies of chair, half-chair, and boat conformations of 1,6-diazabicyclo[4.1.0]heptanes are equalized.     

From D-glucose to biologically potent L-hexose derivatives: synthesis of alpha-L-iduronidase fluorogenic detector and the disaccharide moieties of bleomycin A2 and heparan sulfate

A novel and convenient route for the synthesis of biologically potent and rare L-hexose derivatives from D-glucose is described. Conversion of diacetone-alpha-D-glucose (14) into 1,2:3,5-di-O-isopropylidene-beta-L-idofuranose (19) was efficiently carried out in two steps. Orthogonal isopropylidene rearrangement of compound 19 led to 1,2:5,6-di-O-isopropylidene-beta-L-idofuranose (27), which underwent regioselective epimerization at the C3 position to give the L-talo- and 3-functionalized L-idofuranosyl derivatives. Hydrolysis of compound 19 under acidic conditions furnished 1,6-anhydro-beta-L-idopyranose (35) in excellent yield, which was successfully transformed into the corresponding L-allo, L-altro, L-gulo, and L-ido derivatives via regioselective benzylation, benzoylation, triflation and nucleophilic substitution as the key steps. Applications of these 1,6-anhydro-beta-L-hexopyranoses as valuable building blocks to the syntheses of 4-methylcoumarin-7-yl-alpha-L-iduronic acid and the disaccharide moieties of bleomycin A(2) as well as heparan sulfate are highlighted.     

Intramolecular Diels—Alder reaction of 4-(N-furfuryl)aminobut-1-enes. New approach to the synthesis of 6,8a-epoxyoctahydroisoquinoline (3-aza-11-oxatricyclo[6.2.1.01,6]undec-9-ene) derivatives

The intramolecular Diels—Alder reaction of readily accessible 4-substituted 4-(N-furfuryl)aminobut-1-enes was studied and a new one-step method was developed for the synthesis of 6,8a-epoxy-1,2,3,4,4a,5,6,8a-octahydroisoquinoline (3-aza-11-oxatricyclo[6.2.1.0^1,6]undec-9-ene) derivatives. The [4+2]-cycloaddition proceeds stereoselectively to form exo-adducts. The influence of substituents at the nitrogen atom in 4-(N-furfuryl)aminobut-1-enes on the cycloaddition pathway was examined.     

Synthesis ofS-(+)-hydroprene

A novel path toS-(+)-hydroprene (1) starting from the technical gradeS-(+)-dihydromyrcene (2, e.e. 50%) is proposed. The latter was selectively transformed intoS-3,7-dimethyloctanal (5) in three steps including hydroalumination. The reactions of5 with allyl- or methallylmagnesium chloride followed, respectively, either by oxygenation in the presence of PdCl₂/CuCl or by ozonolysis, affordS,E-6,10-dimethyl-3-undecen-2-one (7) which was treated with ethoxyethynylmagnesium bromide to give the title juvenile hormone analogue in 23% overall yield.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No 1, pp. 110–112, January, 1993.     

Pericyclic and Heteroelectrocyclic Mechanisms for the Cyclization of 1,3,5-Hexatrien-1-one and Its 6-Aza Analog

The cyclization of 1,3,5-hexatrien-1-one, 1, and the Z- and E-isomers of 1-aza-1,3-butadienylketene 3 were studied using the semiempirical AM1 and PM3 methods. Cyclizations of compounds 1 and Z-3 are shown to occur via a mono-rotation mechanism with barriers of 15.49 and 32.85 kcal/mol respectively. The reactions proceed via non-planar transition states which result from rotation of the methylene group for compound 1 and the imino group for compound Z-3. Cyclization of E-3 proceeds via a non-rotatory mechanism through a planar transition state. The activation barrier is 4.83 kcal/mol (AM1). The electronic structures of the initial and final states, and of some intermediate structures, including the transition states for the cyclization of compounds 1 and 3, were analyzed by the natural orbital method using HF/6-31G*//AM1 calculations. Energetic, structural, and orbital criteria indicate the heteroelectric mechanism for the cyclization of compound E-3 and the pericyclic mechanism for the cyclization of compounds 1 and Z-3.     

Vibrational Spectroscopic Studies on the Hofmann Type Clathrates: M(1,6-diaminohexane)Ni(CN) 4 .G (M = Co, Ni or Cd; G = chlorobenzene, 1,2-, 1,3- or 1,4-dichlorobenzene)

New Hofmann-diaminohexane(dahxn)-type clathrates of the form M(1,6-dahxn)Ni(CN)₄.G (M = Co, Ni or Cd; G = chlorobenzene, 1,2-, 1,3 or 1,4-dichlorobenzene) were prepared inpowder form and their infrared spectra are reported. The spectral data suggest that these compounds are similar in structure to those of the Hofmann-diam-type clathrates. Their structure consists of planar polymeric layers, {M–Ni(CN)₄}, formedfrom Ni(CN)₄ anions coordinated to the bridging 1,6-diaminohexane molecules bound directly to the metal (M). The M atoms are bound to four N atoms of the CN ions and, the Ni atoms are surrounded by four C atoms of the CN groups in a square-planar layer.     

Oxazoline as a useful tool in organic synthesis: preparation of 4-aryl-1,2,3,4-tetrahydroisoquinoline alkaloid skeleton

New direct strategy for the synthesis of 4-aryl-1,2,3,4-tetrahydroisoquinolines. The key steps are based on oxazoline chemistry: nucleophilic substitution in an ortho-methoxyphenyloxazoline with a Grignard reagent and a 1,6-conjugate addition of a lithium amide to o-styrylphenyloxazoline.     

On the tautomerism of hypericin: The 1,6-dioxo tautomer

Summary The 1,6-dioxo-tautomer of hypericin was obtained by basic and BF₃ catalyzed tautomerization of the natural and most stable 7,14-dioxo-tautomer. The isolation of this tautomer was aided by its insolubility in methanol. It was identified and characterized by spectroscopic methods, and its detailed structure was derived by means of force field calculations.

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Zur Tautomerie des Hypericins: Das 1,6-Dioxo-Tautomere

Zusammenfassung Das 1,6-Dioxo-Tautomere des Hypericins wurde durch basen- und BF₃-katalysierte Tautomerisierung des natürlichen, stabilen 7,14-Dioxo-Tautomers erhalten. Dessen Isolierung wurde durch die Schwerlöslichkeit in Methanol ermöglicht. Es wurde durch spektroskopische Methoden identifiziert und charakterisiert, und seine detaillierte Struktur wurde aus Kraftfeld-Rechnungen abgeleitet.