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.     

Photodiffraction in InGaAs/InGaAsP multiple quantum wells enclosed in a microcavity

We report new results on the diffraction properties of photoinduced gratings in InGaAs/InGaAsP MQW structures. The original feature of this device is that the QWs are enclosed in an asymmetric Fabry–Perot microcavity in order to increase the diffraction efficiency. We observe oscillations in the diffraction efficiency due to resonant effects in the microcavity. The experimental spectra are compared with theory. Diffraction efficiency at 1.55 μm attains a maximum value of 2.7% at a write beam fluence of 260 μ J cm⁻², and then decreases at higher fluences. We explain this phenomenon by an absorption saturation at high excitation.     

Backward extensions of subnormal operators

The concept of backward extension for subnormal weighted shifts is generalized to arbitrary subnormal operators. Several differences and similarities in these contexts are explored, with emphasis on the structure of the underlying measures.

     

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.     

Infinite products for power series

An algorithm is introduced and shown to lead to a unique infinite product representation for a given formal power series A(z) with A(0) = 1. The infinite product is , where all b_n ≠ 0, r_n , and r_n+1 > r_n. The degree of approximation by the polynomial (1 + b₁z^r₁) · · · (1 + b_nz^r_n) is also considered.