3-Bromo-2-(tert-butylsulfonyl)-1-propene. A multi-coupling reagent Part 1.

3-Bromo-2-(tert-butylsulfonyl)-1-propene $\text{4}$ is easily available in two steps from allyl-tert-butylthioether $\text{5}$ (70% overall yield). It reacts with a great variety of carbanions to give functionnalized α, β-unsaturated sulfones of type $\text{7}$ in high yields. A second nucleophile (lithium cuprates) can then be added to compounds $\text{7}$ to furnish functionnalized sulfones of type $\text{3}$ (Y=SO₂-tert-butyl).     

An organocopper mediated synthesis of (E)-1,4-di-tert-butylbutatriene.

In the paper a highly stereoselestive route to $\text{trans}$-1,4-di-tert-butylbutatriene $\text{via}$-$\text{t}$-BuCu induced 1,3-substitution in ($\text{Z}$)-$\text{t}$-BuCHC(Br)CCH is described.     

Stereochemistry of bis-(dichlorocyclopropanation) and -(epoxidation) of 1,4-diarylbutadienes

Dichlorocyclopropanation as well as epoxidation of the 1,4-diarylbutadienes $\text{1}$-$\text{4}$ to give the mono- and/or bisadducts according to several hindrance of large substituents as 2,6-dichlorophenyl. The bisadducts are formed preferably as $\text{meso}$- (or $\text{threo}$-) isomers.     

Ring-chain isomeric transformations. The cyclohemiketal structure of 4,4,4-trifluoro-1-(2-hydroxyphenyl)-1,3-butanediones

Compounds $\text{4}$-$\text{8}$ exist only in the cyclohemiketal form both in the solid state and in solution, in contrast with earlier assumptions on their enolic structure.     

Terpenes and terpene derivatives - XV. [1 ] Synthesis of 4,8-dimethyl-2-(2-methyl-1-propenyl)--1-oxaspiro(4.5]dec-7-ene (“bisabolene oxide”)

Starting from the ketones $\text{3}$ and $\text{4}$ the synthesis of six spiro ethers with an l-oxaspiro[4.5]decane skeleton is described. Five of them, $\text{9a}$,$\text{b}$, $\text{10a}$,$\text{19}$ and $\text{19}$ represent typical partial structures of the sesquiterpenoid spiro ether $\text{1}$. The unambiguous synthesis of $\text{1}$ shows a previous assignment of “'bisabolene oxide“' to structure $\text{1}$ to be wrong.     

(E)- and (Z)-1-benzenesulfonyl-4-trimethylsilyl-2-butenes as (E)-1-(1,3-butadienyl) synthons

(E)- and (Z)-1-benzenesulfonyl-4-trimethylsilyl-2-butenes (E/Z=9), prepared from 4-trimethylsilyl-1-buten-3-ol, $\text{n}$-butyllithium and benzenesulfenyl chloride and oxidation of the intermediate (E)- and (Z)-1-benzenesulfinyl-4-trimethylsilyl-2-butenes with hydrogen peroxide, react with $\text{n}$-butyllithium and then primary halides to give 4-benzenesulfonyl-1-trimethylsilyl-2-alkenes which are rapidly 1,4-debenzenesulfonyltrimethylsilated to (E)-1,3-alkadienes by tetra-$\text{n}$-butylammonium fluoride at O°C.     

1,5-Bis(trimethylsiloxy)-1,5-dimethoxy-1,4-pentadienes. cyclopropane synthesis via intramolecular coupling.

The title compounds ($\text{1}$a–e) can be prepared in good yield by silylation of the dianions of dimethyl glutarates ($\text{2}$a–e). On treatment with titanium tetrachloride, they cyclise stereoselectively to dimethyl $\text{trans}$-cyclopropane-1,2-dicarboxylates.     

Formation of benzo[a]phenoxazine derivatives by triethylphosphite-induced deoxygenation of 1-(2-nitrophenoxy) and 2-(2-nitrophenoxy)naphthalenes

Reaction of 1-(2-nitrophenoxy)naphthalene or its β-isomer $\text{7}$ with triethylphosphite produces benzo[a]phenoxazines $\text{8}$ and $\text{10}$, through the intermediate $\text{6}$.     

Kationische cyclisierung von (Z)-und (E)-1,3-dimethyl-2-(3-hexenyl)-2-cyclohexenol

The cationic cyclization of the carbinol $\text{3a}$(Z) occurred stereoselectively and resulted in a mixture of the hydrindane $\text{4a}$ and the octalin $\text{5a}$, both with $\text{trans-}$configuration of side chain and angular methyl group. Cyclization of $\text{3b}$(E) yielded in $\text{4b}$ and $\text{5b}$, both with $\text{cis}$-configuration. The structure of $\text{4a}$,$\text{5a}$ was proved by transformation to the diketones $\text{8}$,$\text{9}$.     

Stereoselective synthesis of 3-(1-Hydroxyethyl)-2-azetidinonesfrom 3-hydroxybutyrates

Addition of dianions of 3-hydroxybutyrates to benzylideneaniline results in direct formation of $\text{trans}$$\text{S*}$-3-(l-hydroxyethyl)-1,4-diphenyl-2-azetidinone with 95% diastereoselectivity. Inversion of the configuration at Cα, gives the desired $\text{trans}$$\text{R*}$-2-azetidinone in high yield.     

Leitfähigkeit dotierter (μ-1,4-diisocyanobenzol)phthalocyanina toeisen(II)-verbindungen

Conductivity of doped (μ-1,4-diisocyanobenzene)phthalocyaninatoiron(II)-compounds. - The (μ-1,4-diisocyanobenzene)phthalocyaninatoiron(II)-compounds $\text{2a}$, $\text{3a}$, $\text{5a}$ and $\text{6a}$ are doped with iodine leading to air stable powders which are stable up to 100°C. They were characterized by elemental analyses, TGA/DTA, IR-, resonance Raman- and ⁵⁷Fe-Mössbauer spectroscopy. Increasing dopant levels result in higher electronic conductivities up to 10^?2 S/cm and in decreasing activation energies.     

3-Bromo-2-(tert-butylsulfonyl)-1-propene. A multi-coupling reagent. Part 2. <1

3-bromo-2-(tert-butylsulfonyl)-1-propene 1 reacts in good yields with various electrophiles (aldehydes, ketones, nitriles and alkynes) in the presence of zinc metal to give unsaturated sulfones of type 4. These compounds can further react with soft or hard nucleophiles (alkyl-, vinyl-, aryllithium compounds, a nitroparaffin or dimethylmalonate) to yield highly functionnalized sulfones of type 5 which can be readily transformed into enones or into a dienone. Thus sulfone 1 is a versatile multi-coupling reagent which is synthetically equivalent to the $\text{a}{}^2\text{a}{}^{\mathrm{2\prime }}$ synthon 8 and to the $\text{d}{}^2\text{d}{}^{\mathrm{2\prime }}$ synthons 9 and 10.     

Nucleophilic reactions of fluoroolefins. I. Reactions of 1-(2-tetrahydrofuryl)-pentafluoropropene with alkoxide ions

Unlike unsubstituted perfluoropropene [1,2] 1-(2-tetrahydrofuryl)-pentafluoropropene $\text{1}$ reacts with sodium alkoxides in parent alcohol solutions to give 1-alkoxy-1-(2-tetrahydrofuryl)-tetrafluoropropenes $\text{2}$ as major products and 1-alkoxy-2H-1-(2-tetrahydrofuryl)-pentafluoropropanes $\text{3}$ as very minor products. The yield of adducts $\text{3}$ is, to some extent, increased by the reduced basicity of the alkoxide ion. Results are discussed in terms of the supposed properties of the carbanionic intermediates involved.N.m.r., m.s., and i.r. data for, and some chemical properties of compounds $\text{2}$, viz., further reactions with sodium alkoxides and hydrolysis are described.     

Syntheses and thermal reactions of 2-alkyl(or aryl)-1-benzoyl-3,4-dihydro-2-thianaphthalenes

1-Benzoyl-2-methy1-3,4-dihydro-2-thianaphthalene ($\text{4a}$) underwent novel intermolecular 1,4-rearrangement in refluxing toluene to give an enol ether $\text{5a}$, while rearrangement of 2-phenyl derivative $\text{4e}$ proceeded intramolecularly in refluxing xylene to afford a 1,4-rearranged enol ether $\text{5b}$. On the other hand, ylides $\text{4a–e}$ were refluxed in alcohols to afford some ring-opened products $\text{10–12}$.     

Structure of trans-chloro-1,4-bis(ϱ-methoxyphenyl)-1,4-diaza-3methylbutadiene-2-yl-bis(triphenylphosphine)-palladium(II)

The structure of the compound trans-[PdCl {$\text{C(N-?-C}{}_6\text{H}{}_4\text{OMe)C}$(Me)N-?-C₆H₄OMe} (PPh₃)₂] was solved, using a conventional combination of Patterson and Fourier functions, least-squares refinements and electron density difference maps, to a reliability index R of 0.069 for the 2923 observed reflections collected by four-circle diffractometer. The palladium arom is surrounded in a roughly planar fashion by two trans phosphorus atoms, a chlorine atom, and a σ-bonded carbon atom of the diazabutadienyl group. This group assumes a trans configuration, the NCCN fragment being virtually planar and nearly normal to the mean coordination plane. The Pdligand bond lengths are: PdC 1.98(1), PdCl 2.41(1),PDP(1) 2.33(1) and PdP(2) 2.35(1) Å.     

1-phenyl-3-(trifluormethansulfonyl)-propadien

For the first time a perfluoroalkanesulfonylallene, the 1-phenyl-3-(trifluoromethanesulfonyl)-propadiene ($\text{5}$) was synthesized. $\text{5}$ is $\text{5}$ reacts already at room temperature with cyclopentadiene to form the adduct $\text{6}$.     

Synthesis of 1-[(2-hydroxy-1-(hydroxymethyl)ethoxy)methyl]-1,2,4-triazole-3- and 5-carboxamides

Coupling of trimethylsilyl derivative of methyl 1,2,4-triazole-3-carboxylate with 2-$\text{O}$-(chloromethyl)-1,3-di-$\text{O}$-benzyl glycerol, followed by amination and removal of the protecting groups afforded 1-[(2-hydroxy-1-(hydroxymethyl)ethoxy)methyl]-1,2,4-triazole 3- and 5-carboxamides, 1a and 1b, respectively.     

Studies on phosphonic acid antibiotics. II. Synthesis of 3-(n-acetyl-n-hydroxyamino)-2(r)-hydroxypropylphosphonic acid (FR-33289) and 3-(n-formyl-n-hydroxyamino)-1-trans-propenylphosphonic acid (FR-32863)

The syntheses of FR-33289 ($\text{3}$), originally isolated from a microorganism, and FR-32863 ($\text{6}$), first designed on the basis of a biogenetic consideration and recently found to be also present in nature, are described.     

Synthesis of (±)-1-desoxy-2-lycorinone and of a possible trans-dihydro-lycoricidine precursor

En-route from the 5-aryl-3-hydroxy-4-nitro-cyclohexanones $\text{1}$ and $\text{2}$, readily available from poly-enolates and 3.4-methylenedioxy-w-nitro-styrene, to dihydro-lycoricidine $\text{3}$ and to lycorine $\text{4}$, respectively, the title compounds $\text{9}$ and $\text{14}$ are prepared in few steps.     

Heterocyclic polyfluoro-compounds. Part 35 [1] dehydrofluorination of 2,2-bis(trifluoromethyl)- and 2-perfluoroalkyl-3,4-difluoro-oxetans

Solid potassium hydroxide dehydrofluorinates 2,2-bis-(trifluoromethyl)-3,4-difluoro-oxetan to 3-fluoro-4,4-bis-(trifluoromethyl)-2-oxete (59%), 2-pentafluoroethyl-3,4-difluoro-oxetan to 2-tetrafluoroethylidene-3,4-difluoro-oxetan, and $\text{r}$-2-heptafluoro-n-propyl-$\text{t}$-3,$\text{t}$-4-difluoro-oxetan to ($\text{Z}$)-2-hexafluoro-n-propylidene- $\text{cis}$-3,4-difluoro-oxetan. Factors which affect these reactions are discussed.