Singlet oxygenation of cycloheptatriene: isolation and characterization of the 1,2-dioxetane

Tetraphenylporphyrin-sensitized photooxygenation of cycloheptatriene afforded the 1,2-dioxetane ($\text{3a}$) in 9% yield, thus completing the set of possible cycloaddition products; the 1,2-dioxetane ($\text{3a}$) is the precursor to the benzaldehyde product, but not the (2+6)-cycloadduct ($\text{2a}$).     

The resolution of racemic 2-alkyl-1-aminocyclopropane-1-carboxylic acids

Practical procedures for the resolution of racemic modification of (1$\text{R}$, 2$\text{S}$)-and (1$\text{S}$, 2$\text{R}$)-1-amino-2-ethylcyclopropane-1-carboxylic acid $\text{1a}$,$\text{b}$,(1$\text{R}$, 2$\text{S}$)- and (1$\text{S}$, 2$\text{R}$)-1-amino-2-methylcyclopropane-1-carboxylic acid $\text{2a}$,$\text{b}$, and (1$\text{R}$, 2$\text{R}$)- and (1$\text{S}$, 2$\text{S}$)-1-amino-2-methylcyclopropane-1-carboxylic acid $\text{3a}$,$\text{b}$ are described; the structures as $\text{1a}$,$\text{2a}$, and $\text{3a}$ were confirmed by X-ray-crystallographic methods.     

Stereoselektive synthese von α-glucosiden mit 1,1′ -diacetal-struktur

Reaction of ($\text{1b}$) and ($\text{1d}$) with the acetal ($\text{2a}$) in presence of trimethylsilyl trifluoromethanesulfonate at ?70° C gives the α-glucosides ($\text{3a}$) and ($\text{4a}$), whereas ($\text{1a}$) and ($\text{1c}$) lead to the β-glucosides ($\text{4c}$) and ($\text{4b}$). At 0° C reaction of ($\text{1a}$) with the acetals ($\text{2b-g}$) gives exclusively the α-glucosides ($\text{3b-g}$).     

Synthesis and physical properties of 6,12-diarylazuleno[1,2-b]azulenes

The structure of a minor dimer ($\text{2a}$) of 1-arylcycloheptatrienylidenethylene was determined by X-ray crystallography. Dehydration of $\text{2a}$ and $\text{2b}$ gave novel non-benzenoid aromatics---6,12-diarylazuleno[1,2-b]azulenes ($\text{3a}$ and $\text{3b}$), whose electronic and NMR spectral properties were reported.     

The [4.4.4.4]Fenestranes and[2.2.2.2]paddlane. Prospects for the realization of planar tetracoordinate carbon?

Semi-empirical (MINDO/3 and UNDO) MO calculations on highly strained planar tetracoordinate carbon candidates indicate the central carbons in $\text{cis}$- [4.4.4.4] fenestrane ($\text{1}$) to have pyramidal ($\text{1a}$) and in trans-[4.4.4.]fenestrane ($\text{2}$) to have distorted tetrahedral ($\text{2a}$) geometries. In [2.2.2.2]paddlane ($\text{3}$), the two central carbons are pentacoordinate. Each is nearly coplanar with four carbon neighbours; additionally, the two bridgehead carbons are connected by a single bond ($\text{3a}$).     

Oxidative decarboxylation of [n.2.2]propellane carboxylic acids with lead tetraacetate. rearrangement approach to bicyclo [n.2.2.]bridgehead alkenes.

Oxidative decarboxylation of [n.2.2]propellane carboxylic acids ($\text{1a}$-$\text{c}$) with lead tetraacetate gave the bicyclic acetates ($\text{2b}$, $\text{c}$) having a bridgehead double bond and/or the tricyclic acetates ($\text{3a}$, $\text{b}$) in good yields. Vapor phase thermolysis of $\text{3a}$ or $\text{3b}$ afforded the bridgehead olefin $\text{2a}$ or $\text{2b}$ quantatively.     

Synthesis of silyl-substituted vinylallenes

The coupling between the 5-chloro-3-en-1-ynes $\text{1a}$ - $\text{1e}$ and trimetylchlorosilane gives rise to the vinylallenes $\text{2a}$ - $\text{2e}$ substituted by a trimethylsilyl group on the allenic moiety.     

Perhalogenmethylmercapto-heterocyclen,IX (perchlormethylmercapto)- und (perfluormethylmercapto)pyridine

Methods of substituting pyridine by perhalogenomethylmercapto groups are discussed. The side chain chlorination of 2-(methylmercapto)pyridine leads gradually to 2-(trichloromethylmercapto)pyridine hydrochloride ($\text{1a}$) and 2-(trichloromethylmercapto)pyridine ($\text{1b}$). Neither a direct reaction of pyridine with CF₃SCl nor the way over a Grignard reaction or a sulfenylcarboxylate lead to CF₃S-substituted products. Reactions of pyridine and bromopyridines with Hg(SCF₃)₂ yield 1:1-adducts ($\text{2a-d}$) only. Lithium tetrakis(1,2-dihydro-1-pyridyl)aluminate (LDPA) reacts with CF₃SCl to give 3-(trifluoromethylmercapto)pyridine ($\text{3}$); in addition a disubstituted product can be identified massspectroscopically. ¹H- and ¹⁹F-NMR-spectra are reported.     

A nitrosamine route to (±)-macrostomine

In a synthetic approach to macrostomine $\text{1}$, both side chains of the isoquinoline nucleus are attached by high yield carbon carbon bond formation with lithiated nitrosamines ($\text{2b}$ → $\text{3a}$, $\text{3c}$ → $\text{4a}$).     

Aromatisierung von cytclohexenon-derivaten über selenorganische zwischenstufen

Reaction of the hydroaromatic compounds ($\text{1a}$) and ($\text{3a}$) with lithium-diisopropylamide followed by phenylselenenyl chloride gives the selenides ($\text{1b}$) and ($\text{1c}$) resp. ($\text{3b}$), which form exclusively the phenols ($\text{4}$) resp. ($\text{6}$) after oxidation with 3-chloroperbenzoic acid in the presence of 3,5-dimethoxyaniline ($\text{7a}$).     

Novel fluoride transfer in the reaction of tricyclic epoxides with boron trifluoride

Reaction of the tricyclic epoxides ($\text{1a}$) and ($\text{1b}$) with boron trifluoride etherate leads to fluorohydrins ($\text{2a}$) and ($\text{2b}$) derived in the novel fluoride transfer, whereas ($\text{1c}$) undergoes isomerization to spiro ketone ($\text{3}$).     

A convenient synthesis of erythro- and threo-3-fluorophenyl- alanine from a protected glycine synthon

A facile synthesis of the title compounds ($\text{8}$ and $\text{9}$) is described; key steps include the mono-C-alkylation of the glycine Schiff base benzyl ester $\text{1a}$ with α-bromo-α-fluorotoluene, which provides the readily separable fluorinated diastereomers $\text{2a}$ and $\text{3a}$, and the dealkylative hydrolysis of the benzyl esters $\text{2a}$-$\text{5a}$ without concomitant loss of the benzylic fluorine.     

Generation and reactivity of bis(2,6-diethylphenyl)germanium(II)

The title intermediate ($\text{3a}$) is produced on photolysis of hexakis(2,6-diethyl-phenyl)cyclotrigermane ($\text{1}$) or bis(2,6-diethylphenyl)bis(trimethylsilyl)germane ($\text{4}$) as evidenced by trapping experiments, and thermally dimerizes to tetrakis(2,6-diethyl-phenyl)digermene ($\text{2a}$). Diarylgermylenes such as $\text{3a}$ do not form stable triethylamine adducts (e.g. $\text{5a}$) as has been previously reported.     

Facile syntheses of 2,4,6-cycloheptatrienyl ketones

The synthesis of the 2,4,6-cycloheptatrienyl ketones $\text{1a}$–$\text{1e}$ by two alternative routes is reported: Route 1): The adducts $\text{3a–c}$ from the phenyl(trimethylsiloxy)-acetonitriles $\text{2a–c}$, known as “umpolung” reagents, and tropylium tetrafluoroborate are cleaved by triethylammonium fluoride to form the aromatic cycloheptatrienyl ketones $\text{1a}$–$\text{1c}$. Route 2): the phenyl, methyl, and cyclopropyl ketone ($\text{1a}$, $\text{1d}$, $\text{1e}$) are prepared by treatment of the acid chloride $\text{7}$ with the corresponding organomanganese iodides RMnI ($\text{8a}$, $\text{8d}$, $\text{8e}$). The Fe-catalyzed coupling reaction of the acid chloride $\text{7}$ with a Grignard reagent was also used for the preparation of ketone $\text{1b}$.     

An unusual chlorination of 1-phenyl-4-(2,6-dichlorophenyl)-1,3-butadiene

The diene $\text{1a}$ reacted with CHCl₃/aq. NaOH/PTC in CH₂ Cl₂ unexpectedly to give a mixture of the chlorination products $\text{2}$ and $\text{3a}$. Usual chlorination with Cl₂ yielded similarly $\text{2}$, $\text{3a}$, and $\text{3b}$ dependent on the amount of Cl₂. The formation of $\text{2}$ as well as the reaction of $\text{7}$ to give $\text{9}$ (besides $\text{8}$) shows an unusual Cl-Cl-interaction.     

Photochemistry of N-aryl-2(1H)-pyrimidin-2-ones

Irradiation of N-aryl-2(1H)-pyrimidin-2-ones ($\text{3a}$-$\text{c}$) in a mixed benzene-alcohol solution afforded the products initiated by Type I cleavage, 1-(3-alkoxycarbonylamino-2-propene)-N-arylimines ($\text{4a}$-$\text{c}$, $\text{5}$, and $\text{6}$) in 45–51% yields.     

Studies on amino acids and peptides VIII : Synthesis and crystal structure of two monothiated analogues of Boc-Gly-S-Ala-Aib-OMe

The model tripeptide Boc-Gly-S-Ala-Aib-OMe ($\text{2b}$) and the two monothiated analogues Boc-Gly(¹ψ²CSNH)-S-Ala-Aib-OMe ($\text{2c}$) and Boc-Gly-S-Ala(²ψ³ CSNH)-Aib-OMe ($\text{2a}$) were synthesized. Peptide $\text{2a}$ was obtained by thiation of $\text{1a}$ using 2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane 2,4-disulfide, Lawesson's Reagent (LR), followed by deprotection of the Boc group and coupling with Boc-Gly-OH. Thiation of $\text{2b}$ with LR regiospecifically transformed the protected tripeptide to the monothiated analogue $\text{2c}$. X-Ray diffraction analysis showed that the type-III β-turn formed by the reference peptide $\text{2b}$ is preserved in the monothiated analogue $\text{2a}$; conversely,the structure of the isomeric tripeptide $\text{2c}$ is partially extended.     

Acid catalyzed isomerization of bicyclic alkenes: a facile betweenanene synthesis

Isomerization of $\text{cis}$-bicyclo[10.8.0]eicos-1(12)-ene ($\text{1a}$) and $\text{cis}$-bicyclo[10.10.0]docos-1(12)-ene ($\text{1b}$) to [10.8]- and [10.10]betweenanene ($\text{2a}$ and $\text{2b}$) has been effected by sulfuric acid. In both cases, the betweenanene isomers were found to predominate at equilibrium (70/30 $\text{2a}$/$\text{1a}$ and 95/5> $\text{2b}$/$\text{1b}$).     

Amino substituted 1-oxa-3-azabutatrienium salts: preparation, structure and reaction with carbonyl compounds

N,N-Dimethylformamide ($\text{4a}$) and N,N-dimethylpivalamide ($\text{4b}$) react with carbonyl chloride isocyanate ($\text{5}$) in the presence of antimony pentachloride to afford the amino substituted 1-oxa-3-azabutatrienium hexachloroantimonates $\text{6a}$,$\text{b}$. An X-ray diffraction analysis of $\text{6a}$ confirms the proposed structure. The heterocumulenes $\text{6a}$,$\text{b}$ react with aldehydes, ketones and tertiary carboxamides to give the amino substituted 2-azaallenium salts $\text{13a}$-$\text{O}$ in high yields.     

Oxidation of N-hydroxyazetidines: A novel synthesis of N-acetoxy β-Lactams and four-membered cyclic nitrones

The N-hydroxyazetidines $\text{2}$ and $\text{3}$ are prepared startinfrom 2,3-dihydroazete 1-oxides ($\text{1a}$ and $\text{1b}$0 by reduction with sodium borohydride and by reaction with a nucleophile, respectively. The N-thydroxyazetidines $\text{2}$ and $\text{3}$ can be oxidized with mercury (II) oxide to the corresponding nitrones $\text{1}$; oxidation of the N-hydroxyazetidine $\text{2a}$ (unsubstituted at C-4) with $\text{two}$ equivalent of lead tetraacetate tyields the N-tacetoxy β-lactam $\text{4}$.