Oxythallation of norbornene derivatives with thallium(III) acetate in methanol

Treatment of norbornene, norbornadiene, benzonorbornadiene, and chloro- and methoxy-benzonorbornadiene with thallium(III) acetate in methanol affords only the corresponding cis-exo-acetoxythallation adducts in a sharp contrast to oxymercuration of such strained olefins where methoxymercuration prevails. In the cases of substituted benzonorbornadienes the products are obtained as the regioisomeric mixtures, the isomer ratio being determined by ¹³C NMR. In the cases of 5-norbornene-2,3-dicarboxylic anhydride, 5-norbornene-2-methyl-2,3-dicarboxylic anhydride, and 5-norbornen-2-endo-carboxylic acid, lactonization occurs to give a trans-oxythallation adduct having a lactone ring, no introduction of either methoxy or acetoxy groups being observed. ¹H and/or ¹³C NMR data for several new oxythallation adducts are provided. The alkaline sodium borohydride reduction of adducts in methanol affords mainly the parent olefin together with 10–16% yields of the corresponding exo-alcohol.     

Efficient regioselective aldol condensation of methyl ketones promoted by organoaluminum compounds,and its application to muscone synthesis

Regioselective aldol condensation of 2-octanone and 2-butanone at the methyl side proceeded in high yields using a system of dialkylaluminum phenoxide/tertiary amine. The intramolecular aldol condensation of 2,15-hexadecanedione was carried out by the same system, especially di-i-butylaluminum phenoxide/pyridine, to give dehydromuscone in 65% yield. Its hydrogenation afforded muscone (3-methylcyclopentadecanone).     

Autorecycling oxidation of alcohol catalyzed by 1,3,7,9,11,12,14-heptazapentacene-2,4,8,10 (14H,3H,9H,12H)-tetraones (mixed flavins)

1,3,7,9,11,12,14-Heptazapentacene-2,4,8,10 (14$\text{H}$,3$\text{H}$,9$\text{H}$,12$\text{H}$)-tetraones (mixed flavins) were prepared by the cyclization of 1,5-dihydro-8-[N-alkyl-N-(5-nitrouracil-6-yl)-amino-5-deazaflavins with Vilsmeier reagent. The mixed flavins oxidized alcohol under neutral condition in sunlight and a remarkable autorecycling was observed.     

Macrocycles in the construction of acyclic stereochemistry

The conformations of macrocyclic intermediates provide a useful medium through which distant chiral centers may control chemical reactions. In this paper, we show that macrocycles made by cyclization of simple acyclic starting materials with an auxiliary spacer may be used to prepare stereochemically complex acyclic products.     

Local Subexponentiality and Self-decomposability

The class of exponential tilts of convolution equivalent distributions is determined. As a corollary, the local subexponentiality of one-sided infinitely divisible distributions is characterized. It is applied to the subexponentiality of the densities of a self-decomposable distribution and its Lévy measure. Bondesson’s conjecture on the density of the Lévy measure of a lognormal distribution is solved as an example. Results of Denisov et al. on the distributions of random sums are extended to the two-sided case. Finally, the local subexponentiality of the distribution of the supremum of a random walk is characterized.     

Smallness of fundamental groups for arithmetic schemes

The smallness is proved of étale fundamental groups for arithmetic schemes. This is a higher dimensional analogue of the Hermite-Minkowski theorem. We also refer to the case of varieties over finite fields. As an application, we prove certain finiteness results of representations of the fundamental groups over algebraically closed fields.     

Differences in the reaction of electron deficient olefins with organocopper(I)-Lewis acid reagents and evidence for a dianionic equivalent

Treatment of diethyl fumarate and triethoxycarbonylethylene with Bu₂CuLi·AlCl₃ led to 1,4-addition to give butylated products in high yields. In sharp contrast, diethyl maleate and tetraethoxycarbonylethylene predominantly gave the respective reduction products. The first evidence for a presumed dianionic intermediate by trapping with some electrophiles was also presented.