Structural variations among the aporphine-benzylisoquinoline dimers

$\text{Thalictrum}$$\text{minus}$ L. var. $\text{microphyllum}$ Boiss. (Ranunculaceae) has yielded (+)-istanbulamine ($\text{5}$) which is the first aporphine-benzylisoquinoline formed from one (+)-reticuline-type unit linked to a (+)-N-methylcoclaurine moiety. Other new dimers also present are (+)-bursanine ($\text{6}$) and (+)-iznikine ($\text{7}$).     

The absolute configurations of (+)-thalictrifoline and (+)-corydalic acid methyl ester. Total synthesis of (+)-thalictrifoline.

(+)-Thalictrifoline ($\text{3}$) has been synthesized from an optically resolved (+)-8-oxo-13-carboxytetrahydroprotoberberine ($\text{13}$) whose absolute configuration was established by correlation with (+)-$\text{18}$. This determines the absolute configurations of (+)-thalictrifoline ($\text{3}$) as 13R, 14R aria (+)-corydalic acid methyl ester ($\text{9}$) as 3R, 4R.     

Enzymic control of stereochemistry among the Thalictrum bisbenzylisoquinoline alkaloids

The new bisbenzylisoquinolines (+)-tha1igrisine $\text{1}$ and (+)-tha1iphylline ($\text{6}$) have been isolated from $\text{Thalictrum minus}$ var. $\text{microphyllum}$. Four rules are described which correlate the structures of Thalictrum bisbenzylisoquinolines with their stereochemistry at C-1 and C-1'. As a result, (+)-tha1rugosamine is shown to be identical with (+)-homoaromo1ine ($\text{14}$). (+)-Thalisamine and (+)-N'-norhernandezine are also identical and are represented by expression $\text{18}$. The sole exception to the rules is (-)-isothalidezine ($\text{15}$).     

Chiral recognition of alkene and arene hydrocarbons by 1H and 13C NMR. determination of enantiomeric purity

Simultaneous presence of the salt $\text{1}$ and one of the lanthanide complexes (+)-$\text{2}$, (+)-$\text{3}$, or (+)-$\text{4}$ splits ¹H or ¹³C NMR signals of the chiral alkenes $\text{5}$, $\text{6}$, and $\text{8}$ as well as of the chiral arene $\text{7}$; the enantiomeric purity of a mixture of (+)- and (?)-$\text{8}$ was determined successfully.     

Simple camphor derivatives as chiral auxiliaries for asymmetric conjugate addition

The chiral enoates, $\text{4}$, readily available in two simple steps from (+)-camphor, Undergo asymmetric conjugate addition with the Gilman reagent LiBu₂Cu. Chemical yields are high (70–90%) and in the case of the naphthyl-substituted enoate $\text{4e}$ excellent diastereoselectivity (95% $\text{d.e.}$) is observed. 3-Methyl-heptan-l-ol of correspondingly high enantiomeric purity is obtained by reduction of the conjugate adduct with lithium aluminium hydride.     

Chirale synthese von (+)-lycoricidin

The synthesis of (+)-lycoricidine from D-glucose is described. Addition of the carbanion $\text{11}$ to the nitroolefine $\text{10}$ yields the adduct $\text{12}$ + $\text{13}$, from which crystalline lactone $\text{16}$ with $\text{muco}$-configuration in the cyclitol-ring can be isolated after hydrolysis and cyclization. Rearrangement to the lactam $\text{17}$ and elimination yields the (+)-lycoricidine.     

(+)- and (-)-1-0, 4-0-bis(p-chlorobenzyl)threitol as novel resolving agents for optically active anthracyclinone synthesis: an efficient synthesis of optically pure 4-demethoxydaunomycinone

(±)-7-Deoxy-4-demethoxydaunomycinone(±)-$\text{3}$) was cleanly resolved by forming a mixture of the diastereomeric acetals ((?)-$\text{9}$ and (+)-$\text{10}$ or (+)-$\text{9}$ and (?)-$\text{10}$ with the title $\text{vicinal}$-diol((+)- or (?)-$\text{5}$) to give optically pure (R)(?)-$\text{3}$. The method for racemizing the undesired enantiomer((S)(+)-$\text{3}$) was also explored. Optically pure (+)-4-demethoxydauno-mycinone ((+)-$\text{2b}$) was elaborated from (R)(-)-$\text{3}$ according to the reported reaction scheme.     

Synthesis and absolute configuration of +-lineatin,the pheromone of trypodendronlineatum

A new synthesis of (±), (+)- and (-)-lineatin (3,3,7-trimethyl-2, 9-dioxatricyclo [3.3.1.0^4,7] nonane, $\text{1}$) was achieved. The stereochemistry of (+)-lineatin was established as 1$\text{R}$, 4$\text{S}$, 5$\text{R}$, 7$\text{R}$ by an X-ray crystallographic analysis of an intermediate $\text{1}$$\text{5}$.     

The absolute configuration of tri-o-thymotide and its “cage” clathrate inclusion cavity

The absolute configuration of tri-$\text{o}$-thymotide (TOT) has been determined by X-ray crystal structure determinations of two cage-type clathrate inclusion compounds (+)-TOTS·S-(+)-2-bromobutane and (?)-TOT·RR-(+)-2,3-dimethylthiirane; (+)-TOT has a $\text{P}$ propeller-like configuration     

Synthesis of (+) dictyopterene a constituent of marine brown algae and (+) dictyopterene C′ by chirality transfer of optically active allylic benzoate with palladium (O) catalyst.

The first enantioselective syntheses of (+) dictyopterene A $\text{1}$ and (+)dictyopterene C′ were reported. The key reaction was based on palladium promoted cyclisation of chiral allylic benzoate $\text{5}$ with transfer of chirality (anti attack of the palladium with respect to the leaving group) to give optically active vinylcyclopropane $\text{7}$ with (R) configuration which contains proper functionality for further elaboration into $\text{1}$ and $\text{3}$     

Parviflorine,a glycosidic spirobenzylisoquinoline alkaloid

(+)-Parviflorine ($\text{1}$), found in $\text{Fumaria parviflora}$ Lam. (Fumariaceae), is the first known glycosidic spirobenzylisoquinoline alkaloid. Its acid hydrolysis yields (+)-parfumine ($\text{4}$) and D-glucose. Klyne's rule indicates that $\text{1}$ is a β-D-glucoside. The absolute configuration shown in expressions $\text{1-11}$ is predominant among spirobenzylisoquinolines. A generalization has been drawn between plant source and the oxygenation pattern of ring C for the spirobenzylisoquinoline alkaloids.     

Total synthesis of (+)-pederin. 1. Stereocontrolled synthesis of (+)-benzoylpedamide

(+)-Benzoylpedamide (5), a right half of (+)-pederin (1), was synthesized stereoselectively based on the newly developed method for the synthesis of 1,3-$\text{syn}$-and 1,3-$\text{anti}$-polyols.     

Enantiomers of polarized alkenes: chromatographic enrichment and thermal interconversion

(+)- and (?)-$\text{1}$ as well as (+)- and (?)-$\text{2}$ were partially separated by liquid chromatography on triacetylcellulose; racemizations resulted in the barriers (Table 2) to rotation via planarized transition states.     

Optical resolution of tricarbonyl(1-carboxycyclohexa-1,3-diene) iron and the absolute configuration of the products

Resolution of the acid ($\text{1}$) (shown as the (+)-isomer) into its optically pure (+) and (?) isomers and reduction of the CO₂H yields the 2-Me derivative ($\text{2}$) (shown as the (?)-isomer). The absolute configuration of ($\text{2}$) is defined by conversion of the salt ($\text{3}$) of known configuration into ($\text{2}$) and ($\text{4}$). This is the first resolution leading to preparation of pure complexes of known absolute configuration.     

Studies directed towards the asymmetric total synthesis of antileukemic lignan lactones. Synthesis of optically pure key intermediate and its utility

By the self-immolative asymmetric synthesis, optically pure key intermediate β-piperonyl-γ-lactone (R)-(+)-$\text{6}$ was found to be prepared in reasonable yield from the easily available chiral γ-lactone synthon ($\text{1}$) which had been also reported to give an antipode (S)-(-)-$\text{6}$. The optically pure (R)-(+)-$\text{6}$ was shown to be converted successfully into several optically pure natural lignan lactones.     

Studies related to the synthesis of maytansinoids.

Two approaches to the partial synthesis of C₁–C₅ of a bis-nor maytansinoid $\text{1}$ have been investigated starting on the one hand with (S)-(?)-malic acid and on the other, with D-(+)-ribonolactone.     

Synthesis of optically active pheromones with an epoxy ring, (+)-disparlure and the saltmarsh caterpillar moth pheromone [(Z,Z)-3,6-cis-1-9,10-epoxyheneicosadiene]

(+)-Disparlure $\text{2}$, and the saltmarsh caterpillar moth pheromone enantiomers $\text{1}$ were synthesized and the stereochemistry of the naturally occurring $\text{1}$ was shown to be 9$\text{S}$, 1O$\text{R}$.     

Structure and synthesis of physoperuvine: x-ray crystal and molecular structures of the n-benzoyl derivatives of (±)-3- and (+)-4-methylaminocycloheptanone

Single-crystal X-ray analyses have defined the structures and solid-state conformations of (±)-N-benzoyl-3-methylaminocycloheptanone [(±)-$\text{3}$]and (+)-N-benzoyl-4-methylaminocycloheptanone [(±)$\text{4}$]. Resolution of (±)-[4- methylaminocycloheptanone α 1-hydroxytropane]to yield the (+)-enantiomer. Identical in all respects with the free base from natural (+)-physoperuvine, was achieved via the di-p-toluoyl-(+)-tartrate salt.     

Synthesis of both the enantiomers of sclerosporin and sclerosporal,sporogenic substance of sclerotinia fructicola1

Both the enantiomers of sclerosporin $\text{1}$ and sclerosporal $\text{2}$ were synthesized from (-)-carvone. (4R,9R,10S)-(+)-Sclerosporin and (4R,9R,10S)-(-)-sclerosporal were identified as the natural enantiomers by a comparison of their CD-spectra. An intramolecular Diels-Alder route was proved to be an efficient method of preparing sufficient amounts of (+)-$\text{1}$ for the biological study.     

(10R̃, 11R̃)-(+)-squalene-10, 11-epoxide: Isolation from Laurencia okamurai and the asymmetric synthesis

From a red alga $\text{Laurencia okamurai}$ (10$\text{R}\text{?}$, 11$\text{R}\text{?}$)-(+)-squalene-10, 11-epoxide $\text{1}\text{?}$ was isolated and its asymmetric synthesis has been achieved starting from $\text{trans, trans}$-farnesol.