Über die Entstehung von Oligoanthrylen bei der milden Sulfonierung von Anthracen

The sulfonation of anthracene yields a variety of products and byproducts by different reaction paths depending on the reaction conditions. While trying to reduce the number of products formed by sulfonation under mild conditions, a new reaction was found: under certain sulfonation conditions anthracene is not sulfonated but reacts to form oligoanthrylenes. The highest average molecular weight of a fraction, insoluble in benzene, is about 3,000.     

Density functional calculations on Jahn-Teller effect of tetrachloromethane cation

Density functional (DF) calculations of the tetrachloromethane cation and its most important competitive process, the formation of CCl⁺₃, were carried out to explain the possible stability of CCl⁺₄. From results obtained with B-LYP and B-P86 methods, it is possible to produce a slight Jahn-Teller (JT) effect for a C_s planar structure of the cation type CCl₂(SINGLE BOND)Cl(SINGLE BOND)Cl⁺ compatible with the experimental data obtained by electron-spin resonance spectroscopy. A complex of C_3v structure CCl⁺₃(SINGLE BOND)Cl which is similar to the previous one found in CF⁺₄ appears when symmetry-broken wave functions are used in HF-LYP and HF-P86 methods. Depending of the DF method employed, either one of the minima [C_s (planar) and C_3v] is the most stable and competes with the dissociation of the molecular ion to give CCl⁺₃. The JT stabilization energy is smaller when the JT active coordinates are considered. © 1997 John Wiley & Sons, Inc.     

Asymmetric Synthesis of Densely Functionalized Medium‐Ring Carbocycles and Lactones through Modular Assembly and Ring‐Closing Metathesis of Sulfoximine‐Substituted Trienes and Dienynes

An asymmetric synthesis of densely functionalized 7–11‐membered carbocycles and 9–11‐membered lactones has been developed. Its key steps are a modular assembly of sulfoximine‐substituted C‐ and O‐tethered trienes and C‐tethered dienynes and their Ru‐catalyzed ring‐closing diene and enyne metathesis (RCDEM and RCEYM). The synthesis of the C‐tethered trienes and dienynes includes the following steps: 1) hydroxyalkylation of enantiomerically pure titanated allylic sulfoximines with unsaturated aldehydes, 2) α‐lithiation of alkenylsulfoximines, 3) alkylation, hydroxy‐alkylation, formylation, and acylation of α‐lithioalkenylsulfoximines, and 4) addition of Grignard reagents to α‐formyl(acyl)alkenylsulfoximines. The sulfoximine group provided for high asymmetric induction in steps 1) and 4). RCDEM of the sulfoximine‐substituted trienes with the second‐generation Ru catalyst stereoselectively afforded the corresponding functionalized 7–11‐membered carbocyles. RCDEM of diastereomeric silyloxy‐substituted 1,6,12‐trienes revealed an interesting difference in reactivity. While the (R)‐diastereomer gave the 11‐membered carbocyle, the (S)‐diastereomer delivered in a cascade of cross metathesis and RCDEM 22‐membered macrocycles. RCDEM of cyclic trienes furnished bicyclic carbocycles with a bicyclo[7.4.0]tridecane and bicyclo[9.4.0]pentadecane skeleton. Selective transformations of the sulfoximine‐ and bissilyloxy‐substituted carbocycles were performed including deprotection, cross‐coupling reaction and reduction of the sulfoximine moiety. Esterification of a sulfoximine‐substituted homoallylic alcohol with unsaturated carboxylic acids gave the O‐tethered trienes, RCDEM of which yielded the sulfoximine‐substituted 9–11‐membered lactones. RCEYM of a sulfoximine‐substituted 1,7‐dien‐10‐yne showed an unprecedented dichotomy in ring formation depending on the Ru catalyst. While the second‐generation Ru catalyst gave the 9‐membered exo 1,3‐dienyl carbocycle, the first‐generation Ru catalyst furnished a truncated 9‐membered 1,3‐dieny carbocycle having one CH₂ unit less than the dienyne.