Synthesis of silylated methylenecyclopropanes

2-Trimethylsilylmethylenecyclopropane (=3) was synthesized by reaction of lithio methylenecyclopropane with TMSCl. The lithium salt of (=3) reacts with some electrophiles by α- or γ-attack depending on the nature of the electrophile. Whereas alkenylbromides $\text{8}$ and $\text{9}$ or alkinylbromide $\text{10}$ give exclusively α-attack, benzaldehyde reacts with γ-alkylation.     

Regiochemistry of reactions of α-alkoxyallylphosphine oxide ylides with electrophiles.

Anions $\text{4}$, derived from α-methoxyallylphosphine oxides $\text{3}$, react with electrophiles in a highly regioselective fashion to give products of α-attack or γ-attack depending upon the substitution pattern of the ylid $\text{4}$ and the nature of the electrophile.     

Solvent polarity effects on the regioselectivity of photoaddition reactions of arene-ethene systems

Use of polar solvents in the $\text{ortho}$ protocycloaddition of ethenes to anisole greatly increases the regioselectivity of the process and the major adducts reflect 1,2-attack onto the arene.     

Methyl substituent probe of the transition state for thermal decarbonylation of endo-tricyclo[3.2.1.02,4]octan-8-one

Methyl substituent probes at the C-2 and C-2,C-4 positions of $\text{endo}$-tricyclo[3.2.1.0^2,4] octan-8-one($\text{1}$) have provided kinetic evidence confirming the simultaneity of C-2,C-4 cyclopropane bond cleavage in the rate-determining step for thermal extrusion of carbon monoxide.     

The photochemistry of proaporphines: a new route to the aporphines

Proaporphines undergo light catalyzed rearrangement. Pakistanamine ($\text{1}$) is thus converted into lumipakistanine ($\text{2}$), while pronuciferine ($\text{7}$) and N-acetylnorpronuciferine ($\text{8}$) afford the corresponding C-9 hydroxylated aporphines $\text{9}$ and $\text{10}$. Possible biogenetic schemes for the formation of C-8, C-9-, and C-8,9-substituted aporphines are presented.     

Konyanin: a new lignan from hapuophyllum vulcaniclm

Konyanin ($\text{1}$), obtained from $\text{Haplophyllum vulcanicum}$ (Rutaceae), is the first known 1,4-dihydroarylnaphthalene lignan in which the lactone carbonyl is bonded to C-3 rather than to C-2. Detailed NMR spectral data have been complied for the accompanying lignans (-)-kusunokinin ($\text{5}$) and diphyllin ($\text{7}$).     

Completely stereocontrolled synthesis of the right fragment of salinomycin,a polyether antibiotic,by means of the chelation-controlled grignard reaction

In the course of our synthetic study of salinomycin ($\text{1}$), an ionophorous polyether antibiotic, the γ-lactone ($\text{2}$) corresponding to the C-21～C-30 fragment (the right fragment) of $\text{1}$ was synthesized from D-mannitol and ethyl L-lactate as chiral starting materials. The complete stereocontrol for the construction of new chiral centers has been achieved by means of the chelation-controlled Grignard reaction and the tetrahydropyran synthesis via the acid catalyzed epoxide ring opening.     

Synthesis and absolute configuration of A-factor,the inducer of streptomycin biosynthesis in inactive mutants of Streptomyces griseus

The absolute configuration at C-3 of A-factor, 2-(6-methylheptanoyl)-3-hydroxymethyl-4-butanolide $\text{1a}$, was determined to be $\text{S}$ by synthesizing(3$\text{S}$)-(+)-A-factor.     

Nucleophilic reactions of fluoroolefins. II. Regioselectivity and elimination-addition competition in the reaction of 1-phenylpentafluoropropenes with sodium ethoxide

1-Phenylpentafluoropropene and its para-substituted analogs $\text{1}$ are susceptible to nucleophilic attack at both vinylic carbon atoms C-1 and C-2. They react with ethanolio sodium ethoxide to give predominantly substitution products, 1-ethoxy-1-phenyltetrafluoropropenes $\text{2}$ and 2-ethoxy-1-phenyltetrafluoropropenes $\text{3}$, with only little formation of adducts, $\text{viz}$. 2-ethoxy-1H-1-phenylpentafluoropropanes $\text{4}$. Alkenes $\text{1}$, where the para-substituent X  H,Cl,and CF₃ give additionally 1,2-diethoxy-1-phenyltrifluoropropenes $\text{5}$ and, where X = CF₃ also 2,2-diethoxy-1H-1-phenyltetrafluoropropane $\text{6}$. Overall regioselectivity of nucleophilic attack of the ethoxide ion on alkenes $\text{1}$ exhibits the Hammett type correlation with Ó_p values of substituents X: CH₃O and CH₃ groups favour the attack on the vinylic carbon C-1, while CF₃ and Cl substituents direct the attack on the C-2 carbon of alkenes $\text{1}$. The E and Z isomers of 1-ethoxy and 1,2-diethoxy substituted alkenes $\text{2}$ and $\text{5}$ were formed in comparable amounts, while the E isomers of 2-ethoxy substituted alkenes $\text{3}$ were always formed with a 93 – 97 % selectivity.     

Novel rearrangement of twisted 2,4-di-alkyl 2-trans-4-trans pentadienals: An approach to cyclopentenones based on molecular mechanical consideration

Rearrangement of 2,4-di-$\text{trans}$-pentadienals $\text{IVa-d}$ was described as a consequence of the successive alkyl substitutions on the C-2 and C-4 positions. ¹H-FT nmr spectroscopy suggested that the reaction involves ketene $\text{VIII}$ as an intermediate.     

Stereoselective total syntheses of (±)-warburganal and (±)-isotadeonal

A short, stereoselective synthesis of (±)-warburganal ($\text{1}$), its C-9 epimer ($\text{2}$) and the related sesquiterpene dialdehyde (±)-isotadeonal is presented.     

On the question of carbonyl oxide intermediates in the oxygen transfer by furan endoperoxides and bicyclic ozonides: intramolecular trapping experiments

On heating the furan endoperoxide ($\text{2}$) rearranges into the enol ester ($\text{4}$) and the bicyclic ozonide ($\text{3}$) affords instead the rearranged ozonide ($\text{7}$). The process ($\text{2}$) → ($\text{4}$) represents an intramolecular Baeyer-Villiger rearrangement presumably via the dioxirane (D-2), while the process ($\text{3}$) → ($\text{7}$) represents intramolecular trapping of the carbonyl oxide (C-3).     

Stereospecific epoxidation of anthracyclinones: a route to 8(r)-methoxydaunomycinone

Stereoselective epoxidation of $\text{1}$, the 7,8-unsaturated derivative of daunomycinone, followed by $\text{trans}$ opening of the epoxide $\text{2}$, afforded 8(R)-methoxydaunomycinone $\text{6a}$; its configuration at C-8 was determined by chemical correlation and PMR studies.     

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.     

4,6-Thioanhydro-hexopyranosides,synthesis and chemical behaviour of methyl 2-0-p-toluenesulfonyl-4,6-thioanhydro-α-d-gulopyranoside

Methyl 4-0-benzoyl-6-bromo-6-deoxy-α-D-glucopyranoside ($\text{1}$, Figure 1) was converted, via the corresponding ditosylate $\text{2}$, into methyl 2,3-di-0-p-toluenesulfonyl-4-0-benzoyl-6-S-acetyl-6-thio-α-D-glucopyranoside ($\text{3}$) by a selective nucleophilic displacement of 6-bromo-group with thioacetate. Unexpectedly, on treating the compound $\text{3}$ with an excess of sodium methoxide in benzene-methanol (1:1) at room temperature, methyl 2-0-p-toluenesulfonyl-4,6-thioanhydro-α-D-gulopyranoside ($\text{4}$) was obtained in a yield of 84%. In order to determine the structure of the relatively unstable oily product $\text{4}$, some stable crystalline derivatives ($\text{5}$, $\text{6}$ and $\text{7}$) were prepared. Detailed analysis of the ¹H-NMR-spectra (200 MHz) of $\text{6}$ and $\text{7}$ gave the conclusive evidence for the structure of $\text{4}$ A self-imposing mechanism of the clean and smooth transformation of $\text{3}$ to $\text{4}$ is proposed, involving: a) formation of $\text{9}$ (Figure 2) as a crucial intermediate and b) a highly regioselective epoxide opening in $\text{9}$ (at C-4) by an intramolecular nucleophilic attack of the mercaptide anion from C-6.     

Biosynthesis of pebrolide

In pebrolide biosynthesised from MVA-[2.2-³H₂], 1, 1$\text{1}\text{3}$ and 2 tritium atoms respectively are retained at C-1, C-15 and C-7.     

Determination of the absolute configuration at C-6 and C-7 of serricornin (4,6-dimethyl-7-hydroxy-3-nonanone), the sex pheromone of the cigarette beetle

The absolute configuration at C-6 and C-7 of serricornin was established as (6$\text{S}$, 7$\text{S}$) by synthesizing its (6$\text{R}$, 7$\text{S}$-$\text{erythro}$ and (6$\text{R}$, 7$\text{R}$-$\text{threo}$ isomers.     

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 ($\text{15}$).     

Synthesis of Δ1-carbapenem derivative by aldol condensation method

The Δ¹-carbapenem derivative($\text{6}$) was prepared by the aldol condensation of the dialdehydic compound($\text{5}$) with piperidinium acetate. Careful hydride reduction followed by benzoylation gave $\text{7}$b, which was successfully decarbalkoxylated to $\text{8}$. The X-ray structure analysis of $\text{8}$ showed the C-3 carboxylate group and C-5 H are $\text{cis}$ each other.     

Formation of a dinaphthanthracene by a stilbene-like photocyclization

Photocyclization of 1,3-bis[2-(2-naphthyl)vinyl]benzene leads regioselectively to dinaphth[1,2-$\text{a}$:2′,1′-$\text{j}$]anthracene without the need for a blocking bromine substituent at C-2 in the starting material as assumed previously by other workers.