Transition-Metal Catalysis of Triene 6π Electrocyclization: The π-Complexation Strategy Realized

Triene 6π electrocyclization, wherein a conjugated triene undergoes a concerted stereospecific cycloisomerization to a cyclohexadiene, is a reaction of great historical and practical significance. In order to circumvent limitations imposed by the normally harsh reaction conditions, chemists have long sought to develop catalytic variants based upon the activating power of metal–alkene coordination. Herein, we demonstrate the first successful implementation of such a strategy by utilizing [(C₅H₅)Ru(NCMe)₃]PF₆ as a precatalyst for the disrotatory 6π electrocyclization of highly substituted trienes that are resistant to thermal cyclization. Mechanistic and computational studies implicate hexahapto transition-metal coordination as responsible for lowering the energetic barrier to ring closure. This work establishes a foundation for the development of new catalysts for stereoselective electrocyclizations.     

Stable Ergodicity and Frame Flows

In this note we show that all diffeomorphisms close enough to the time-one map of the frame flow on certain negatively curved manifolds are ergodic. As a simple corollary we deduce that the frame flows are ergodic for all compact manifolds with curvature pinched sufficiently close to –1, thus providing results in the case of manifolds of dimension 7 or 8 which were missing from the results of Brin and Karcher.     

Quasi-wavelet calculations of sound scattering behind barriers

Quasi-wavelets (QWs) are a representation of turbulence consisting of self-similar, eddy-like structures with random orientations and positions in space. They are used in this paper to calculate the scattering, due to turbulent velocity fluctuations, of sound behind noise barriers as a function of the size and spatial location of the eddies. The sound scattering cross-section for QWs of an individual size class (eddy size) is derived and shown to reproduce results for the von Kármán spectrum when the scattered energies from a continuous distribution of QW sizes are combined. A Bragg resonance condition is derived for the eddy size that scatters most strongly for a given acoustic wavenumber and scattering angle. Results for scattering over barriers show that, for typical barrier conditions, most of the scattered energy originates from eddies in the size range of approximately one-half to twice the size of the eddies responsible for maximum scattering. The results also suggest that scattering over the barrier due to eddies with a line of sight to both the source and receiver is generally significant only for frequencies above several kilohertz, for sources and receivers no more than a few meters below the top of the barrier, and for very turbulent atmospheric conditions.     

Rational Functions with Prescribed Global and Local Minimizers

A family of multivariate rational functions is constructed. It has strong local minimizers with prescribed function values at prescribed positions. While there might be additional local minima, such minima cannot be global. A second family of multivariate rational functions is given, having prescribed global minimizers and prescribed interpolating data.     

Reactivity of 3-alkyl-4-arylazomethylene-3,4-dihydro-1,2,3-benzotriazines in protic solvents: 1,4-Addition reactions and dimroth rearrangement

3-Alkyl-4-arylazomethylene-3,4-dihydro-1,2,3-benzotriazines 5a and 5b undergo facile 1,4-addition of methanol or ethanol to afford stable crystalline hydrazones, 6 and 8 which have been characterised by spectroscopic analysis. In particular, the nmr spectrum of 8 shows novel features due to the diastereotopic nature of the CH₂ protons in the two O-ethyl groups. Compound 5b shows a property unique to the compounds in this series; refluxing this arylazomethylenetriazine in ethanol affords a rearranged product, characterised as the 1-aryl-2-cinnolinylhydrazine ( 9 ). The formation of 9 is rationalised as a ring opening-ring closure process analogous to the Dimroth rearrangement. The cinnoline 9 displays some novel chemistry arising from the facility of the arylhydrazino substituent to react with acid to give a fragmentation product, 3-methylindazole ( 7 ).     

Steady-state electrolysis at a grooved or ridged plane

This study concerns an infinite plane whose smoothness is marred by a single defect: either a groove or a ridge. The blemished plane serves as an electrode supporting a diffusion-controlled steady-state process. By using a convenient coordinate transformation, the local current density at all points on the surface is determined exactly. The results are found to confirm intuitive expectations. Thus, compared with normal values on the plane remote from a groove, the electron transfer rate is diminished within the groove but enhanced along its margins. Similarly, an abnormally large transfer rate is encountered high on the ridge but the rate is subnormal on its lower flanks. The total current is demonstrated to be unchanged by the presence of the blemish. Received: 27 September 1996 / Accepted: 11 March 1997