The conversion of methylenomycin A to natural botryodiplodin and their absolute configurations

Natural (?)-botryodiplodin($\text{1}$) has been synthesized from an antibiotic methylenomycin A ($\text{2}$). The absolute configurations of (?)-botryodiplodin($\text{1}$ and methylenomycin A ($\text{2}$) have also been established as shown in $\text{1}$ and $\text{2}$ respectively.     

Cyclisierungen unter beteiligung von fluoridionen. 2. Mitteil. [1], [2]. 4.5-perfluor-1.3-dioxolane

4.5-Perfluoro-1.3-dioxolanes $\text{2}$ are available by reaction of 2(α-chloroalkoxy)perfluoro-carbonyl halides $\text{3}$ or -ketone $\text{9}$ with fluoride ions. A mechanism for the intramolecular ring- closure-reaction is proposed. Hydrogen atoms at C-2 in $\text{2}$ can be exchanged photochemically by chlorine. Starting from the 2-monochloro-derivatives $\text{16}$ the 2-monofluoro-4.5-perfluoro- 1.3-dioxolanes $\text{18}$ are formed by reaction with triethylamine- hydrofluoride.     

Stereospecific synthesis of (5E)-PGE2 by palladium-catalyzed decarboxylative 2-alkenylation of 2-alkenyloxycarbonylated cyclopentanone derivative

(5$\text{E}$)-Prostaglandin E₂ methyl ester was synthesized from ($\text{R}$)-4-$\text{t}$-butyldimethylsiloxy-2-cyclopentenone by $\text{in}$$\text{situ}$ 2-alkenyloxycarbonylation of the organocopper conjugate-addition adduct followed by intramolecular palladium-catalyzed decarboxylative 2-alkenylation. A ($\text{E}$)-2-butenylated cyclopentanone derivative was obtained from either 2-[($\text{E}$)- or ($\text{Z}$)-2-butenyloxy-carbonyl]cyclopentanone derivative under the similar reaction condition.     

The unexpected thermal instability of 3,4-tetramethylene-1,2-dioxetane as compared to that of cis-3,4-diethyl-1,2-dioxetane.

3,4-Tetramethylene- and $\text{cis}$-3,4-diethyl-1,2-dioxetane ($\text{1}$ and $\text{2}$) were prepared and characterized (for $\text{1}$ - Ea = 22.5 kcal/mole, log A = 12.8; for $\text{2}$ - Ea = 24.5 kcal/mole, log A = 13.1).     

Synthesis of 2-isopropylfuro(2,3-b)quinolines-a new synthesis of (±)-lunacrine, (±)-lunasine and (±)-demethoxylunacrine

A new and convenient synthesis of 2-isopropylfuro-(2,3-b)quinolines ($\text{4}$) from 3-(3-methylbut-1-enyl)-2-quinolones ($\text{2}$) is described. A neat synthesis of the alkaloids (±)-lunacrine ($\text{1a}$), (±)-lunasine ($\text{12a}$) and (±)-demethoxylunacrine ($\text{1b}$) is also reported.     

New masked building block for isoprenoid polyene chain synthesis

The new building blocks $\text{2}$, $\text{3}$, and $\text{4}$ have been effecively synthesized starting from 2-hydroxymethyl-4-phenylthio-1-butene ($\text{1a}$). A convenient synthesis of retinoic acid methyl ester ($\text{9}$) using $\text{2}$ is also described.     

Synthetic analgesics: preparation of racemic 6,7-benzomorphans

A simple preparation of 2-carbomethoxy-2-azabicyclo[3.3.1]nonan-6-one ($\text{7}$ and its conversion to the racemic benzomorphans: $\text{9}$, $\text{10}$, $\text{14}$ are described.     

Remote inductive effects on secondary and tertiary 2-norbornyl solvolysis rates

A 5-cyano substituent decelerates the solvolysis rate of exo-2-norbornyl brosylate $\text{(1-H)}$ by a factor of 1790. A much smaller deceleration (24–90 fold) is observed for the secondary $\text{endo}$ and for both $\text{exo}$ and $\text{endo}$ tertiary 2-norbornyl derivatives. These results support the occurrence of σ-participation in the solvolysis of $\text{1-H}$.     

Plaunol A and B,new anti-ulcer diterpenelactones from Crotonsublyratus

Two new diterpenelactones named plaunol A ($\text{2}$) and B ($\text{3}$) exhibiting anti-Shay ulcer activity were isolated from Thai medicinal plant, $\text{Croton}$$\text{sublyratus}$. Structure of $\text{2}$ was determined by X-ray analysis of its $\text{p}$-bromobenzoate and structure of $\text{3}$ was deduced from the results of chemical correlation and the spectral data.     

Isolation of aspirochlorine (=antibiotic A30641) possessing a novel dithiodiketopiperazine structure from Aspergillus Flavus

A very unusual dithiokikeptopiperazine structure ($\text{1}$) has been assigned to aspiroclorine, C₉H₁₂N₂O₅S₂Cl, produced as a biologically active substance together with canadensolide by $\text{Aspergillus}$$\text{flavus}$, which has been found to be identical with the antibiotic A 30641 from $\text{A.}$$\text{tamarii}$.     

Synthesis of O-6-alkylated deoxyguanosine nucleosides

A general route for synthesis of 6-$\text{O}$-alkyl-2∝deoxyguanosine nucleosides is described. The key step is conversion of the 6-$\text{O}$-TPS derivative $\text{2}$ to the 6-trimethylamino compound $\text{3}$. The trimethylamino group is readily displaced by alcohols in the presence of DBU. Using this route the 6-$\text{O}$-methyl, ethyl and n-butyl 2∝-deoxyguanosine derivatives $\text{5a-c}$ have been prepared in excellent overall yields.     

Methylated multibridged [2n]cyclophanes. All alternate synthesis of [26](1,2,3,4,5,6) cyclophane (superphane)

A sequence of formylation followed by a carbene insertion reaction has led to the stepwise introduction of additional ethano bridges into 4,5,7,8- tetramethyl [2₂](1,4)cyclophane ($\text{1}$), providing syntheses of 5,7,8-trimethyl- [2₃](l,2,4)cyclophane ($\text{6}$), a mixture of 5,8-dimethyl[2₄(1,2,4,5)cyclophane ($\text{10}$) and 5,7-dimethyl[2₄(1,2,3,5)cyclophane ($\text{11}$, and-4-methyl[2₅](1,2,3,4,5)-cyclophane ($\text{14}$). This route to $\text{14}$ completes a formal eight-step synthesis of [2₆](1,2,3,4,5,6)cyclophane ($\text{15}$, superphane) with an overall yield of 17%. A Birch reduction of $\text{6}$ readily gave 12,15-dihydro-5,7,8-trimethyl[2₃](1,2,4)-cyclophane ($\text{7}$) in 85% yield.     

Synthesis of detoxininolactone derivatives and the revised absolute stereochemistry of detoxinine

A stereospecific synthesis of acetyl-$\text{L}$-valyl-detoxininolactone has been performed and the absolute stereochemistry of detoxinine has been revised to (2$\text{S}$, 3$\text{R}$, 1′$\text{S}$)-2-(2′-carboxy-1′-hydroxyethyl)-3-hydroxypyrrolidine.     

On the claisen rearrangement of 1,4-diaryloxy-2-butynes

A proton nmr follow-up provided conclusive evidence for the involvement of two sequential Claisen rearrangements in the thermal rearrangement of 1,4-diaryloxy-2-butynes $\text{1}$to 11a-methylpterocarpans $\text{3}$. A detailed study of the rearrangement of 1,4-diaryloxy-2-butynes $\text{1}$ in polyethyleneglycol-200 (PEG-200), indicated a definite possibility of selective synthesis of either benzofuron (3,2-b )benzofuran $\text{4}$ or benzofuro(2,3-b)benzofuran $\text{5}$ by varying the temperature of the reaction alone     

Studies directed towards total synthesis of saframycin: I. A synthesis of hexahydro-1,5-imino-3-benzazocin-7,10-dione.

A short-step synthesis of $\text{2}$, the right-hand half of antibiotic saframycin ($\text{1}$), is described. The key steps of this synthesis are the acid catalyzed intramolecular double cyclization of $\text{4}$ and the oxidative demethylation of $\text{7}$ to the quinone ($\text{2}$).     

Inverted and anti-inverted populations of a doublets of chemically produced OH

With the aid of nanosecond laser flash photolysis OH is chemically produced and observed “collision free”. The rotational states show inverted population in the A doublets J = $\text{3}\text{2}$, $\text{5}\text{2}$, $\text{7}\text{2}$, and $\text{9}\text{2}$ of ²Π_{$\text{3}\text{2}$} and anti-i higher rotational states. The intensities of the main and satellite absorption lines further indicate an inversion in special hyperfine states. Application to interstellar OH maser emission is considered.     

Cycloreversion of quadricyclane to norbornadiene catalyzed by Tin (II) complexes

The conversion of quadricyclane ($\text{1}$) to norbornadiene ($\text{2}$) is catalyzed by stannous chloride and stannous chloride-phosphine complexes. A newly synthesized polymer-bound phosphine-stannous chloride complex also proved effective in the catalytic conversion of $\text{1}$ to $\text{2}$.     

Biogenetic-type synthesis of (±)-dictyopterene A,an odoriferous substance obtained from brown seaweeds, Dictyopteris

Biogenetic-type synthesis of (±)-dictyopterene A ($\text{1}$) was achieved employing 1,$\text{cis}$-5-undecadien-3-ol ($\text{2}$) postulated to be a biosynthetic intermediate of $\text{1}$: this synthesis means that transformation of dictyoprolene ($\text{4}$) into dictyopterene A ($\text{1}$) was formally made.     

Rearrangement spinal en serie a/b cis : conversion du lithocholate de methyle en derives du d-homoandrostane

A new backbone rearrangement is observed in A/B $\text{cis}$ methyl lithocholate derivatives. It is initiated from the C-3 carbon either by dehalogenation of the chloroesters $\text{1}$ by AgSbFg₆ or by the action of the triflic anhydride on the si1y1ated ether $\text{2}$. This rearrangement leads to methyl diacholenate $\text{3}$ and new lactones in D-homoandrostane series $\text{5}$ and $\text{6}$. The differences of behaviour between A/B $\text{cis}$ and A/B $\text{trans}$ series and the mechanism of rearrangements are discussed.     

Metabolites of Alternaria solani part V. Biosynthesis of altersolanol A and incorporation of altersolanol A-13Cx into altersolanol B and macrosporin

The biosynthesis of the tetrahydroanthraquinone, altersolanol A ($\text{1}$), by $\text{Alternaria solani}$ has been established by the incorporation of [1,2-¹³C₂]-acetate. A blocked culture of $\text{A. solani}$ was utilized to reveal that $\text{1}$ is metabolized to altersolanol B and macrosporin.