Transannular reactions of two parallel 1,3-butadiynes: syntheses,structures, and reactions of 1-azacyclotetradeca-3,5,10,12-tetrayne derivatives

The synthesis of 1-alkyl and 1-aryl-1-azacyclotetradeca-3,5,10,12-tetraynes was achieved in a stepwise approach. The key intermediate was 1,13-dibromotrideca-2,4,9,11-tetrayne (18). Reaction with methyl- (19 a), ethyl- (19 b), isopropyl- (19 c), n-butyl- (19 d), and tert-butylamine (19 e) as well as aniline (19 f) and p-methoxyaniline (19 g) gave the corresponding 14-membered tetraynes 20 a-20 g. The ring inversion process of 20 b was studied by variable temperature (1)H NMR spectroscopy. From these measurements a value of 10.6 kcal mol(-1) was calculated for DeltaG(not equal). X-ray investigations on single crystals of 20 b, 20 c, and 20 f revealed the axial position for the substituent at each nitrogen atom. For 20 b we encountered the chair conformation, for 20 c both chair and boat conformations, and for 20 f the boat conformation in the solid state. The reaction of 20 c with concentrated HCl in ethanol yielded 2,10-dichloro-6-isopropyl-6-azatricyclo[9.3.0.0(4,8)]tetradeca-1(11),2,4(8),9-tetraene (25 c). Compound 25 c was oxidized by 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) to 27 c. The structure of the latter was confirmed by X-ray investigations. The reaction of 20 c in aqueous HCl lead to the formation of 10-chloro-2-isopropyl-1,3,4,6,7,8-hexahydro-2H-benzo[g]isoquinolin-9-one (37 c). The structure of 37 c was verified by X-ray studies on single crystals.     

Preparation,catalytical activity and crystal structure of a heptanuclear zinc acetate cluster

Reaction of [Zn₄(µ₄-O)(O₂CCH₃)₆] with one equivalent of 4-tertiary-butylpyridine leads to a nearly quantitative formation of the heptanuclear cluster [Zn₇O₂(O₂CCH₃)₁₀(^tbupy)₂] (1). Here, we present the crystal structure of 1 and first results of the examination of its catalytic activity in transesterification reactions and polymerization of lactide compared to the activity of [Zn₄(µ₄-O)(O₂CCH₃)₆] in the presence of 4-tertiary-butylpyridine.     

On the exceptional reactivity of the norbornene double bond

The anomalous reactivity of the bicyclo [2.2.1] heptene double bond is interpreted in terms of hyperconjugative effects, leading to an exceptionally low endo out-of-plane deformation potential.     

Cycloalkadiynes—From Bent Triple Bonds to Strained Cage Compounds

The synthesis of Cycloalkadiynes with medium-sized rings may be accomplished by a number of ring-closing and elimination reactions. Information concerning the conformation of the rings as well as the extent of transannular interaction between the triple bonds is obtained by analysis of X-ray crystallographic data and by photoelectron spectroscopy. The diacetylene complexes of Ag¹ and Cu¹ show hardly any structural change compared to the uncomplexed compounds while the bis(hexacarbonyldicobalt) complexes differ significantly in their structural parameters. Reaction of Cycloalkadiynes with dicarbonyl(η⁵-cyclopentadienyl)cobalt yields inter- and intramolecular cyclobutadiene complexes. The superphane of cyclobutadiene formed by the intermolecular reaction can be transformed into a number of highly strained cage compounds in few steps. In addition, the variety of such cage compounds can be increased if the reaction of a cyclic diacetylene is carried out with dimethylacetylenedicarboxylate in the presence of aluminum chloride. The intermediate bridged Dewar benzenes eventually lead to propellaprismanes.     

Regiochemistry of S-alkyl-substituted alkynes in Pauson-Khand reactions. Is a correlation with X-ray data and charge distribution calculations of the Co(2)(CO)(6)-alkyne complexes possible?

[reaction: see text] Pauson-Khand reactions (PKR) of RSCtbd1;CR' (6-10) yielded in all cases as the main product the regioisomer with the alkyl-S group disposed alpha to the CO group (16a-22a). Correlation of these results with X-ray data and charge distribution calculations of the corresponding dicobalthexacarbonyl complexes proves that a recently postulated "trans effect" in these complexes is not suitable for predicting the regiochemical outcome of the PKR unambiguously.