Asymmetric electrocyclic reactions

This critical review offers an overview of asymmetric electrocyclic processes, where diastereo- or enantioselectivity is a consequence of the influence of a chiral component (be it substrate or catalyst) on the electrocyclic bond-forming process (195 references). © 2011 The Royal Society of Chemistry.

Asymmetric hydrogen flame in a heated micro-channel: role of Darrieus-Landau and thermal-diffusive instabilities

Present work examines numerically the asymmetric behavior of hydrogen/air flame in a micro-channel subjected to a non-uniform wall temperature distribution. A high resolution (with cell size of 25 μm × 25 μm) of two-dimensional transient Navier–Stokes simulation is conducted in the low-Mach number formulation using detailed chemistry evolving 9 chemical species and 21 elementary reactions. Firstly, effects of hydrodynamic and diffusive-thermal instabilities are studied by performing the computations for different Lewis numbers. Then, the effects of preferential diffusion of heat and mass transfer on the asymmetric behavior of the hydrogen flame are analyzed for different inlet velocities and equivalence ratios. Results show that for the flames in micro-channels, interactions between thermal diffusion and molecular diffusion play major role in evolution of a symmetric flame into an asymmetric one. Furthermore, the role of Darrieus–Landau instability found to be minor. It is also found that in symmetric flames, the Lewis number decreases behind the flame front. This is related to the curvature of flame which leads to the inclination of thermal and mass fluxes. The mass diffusion vectors point toward the walls and the thermal diffusion vectors point toward the centerline. Asymmetric flame is observed when the length of flame front is about 1.1–1.15 times of the channel width.

Rational design of a (S)-selective-Transaminase for asymmetric synthesis of (1S)-1-(1,1'-biphenyl 2-yl)ethanamine

Amine transaminases offer an environmentally sustainable synthesis route for the production ofpure chiral amines. However, their catalytic efficiency towards bulky ketone substrates isgreatly limited by steric hindrance and therefore presents a great challenge for industrialsynthetic applications. Hereby we report an example of rational transaminase enzyme design tohelp alleviate these challenges. Starting from the Vibrio fluvialis amine transaminase that has nodetectable catalytic activity towards the bulky aromatic ketone 2-acetylbiphenyl, we employed arational design strategy combining in silico and in vitro studies to engineer the transaminaseenzyme with a minimal number of mutations, achieving an high catalytic activity and highenantioselectivity. We found that by introducing two mutations W57G/R415A detectableenzyme activity was achieved. The rationally designed best variant,W57F/R88H/V153S/K163F/I259M/R415A/V422A, showed an improvement in reaction rateby > 1716-fold towards the bulky ketone under study, producing the corresponding enantiomericpure (S)-amine (ee value of > 99%). 

Studies on the Catalytic Asymmetric Fischer Indolization

This work describes further developments and applications of the catalytic asymmetric Fischer indolization. In the first part of this thesis, the development of an organocatalytic asymmetric synthesis of helicenes via a Fischer indolization is discussed. The application of a novel SPINOL-derived phosphoric acid, featuring extended π-surfaces as 3,3‘-substituents which can potentially participate in π-interactions with the polyaromatic intermediate, afforded the corresponding products in high yields and enantioselectivities. The second part of this work describes the development of a catalytic asymmetric dearomatizing synthesis of 1,4-diketones via an interrupted Fischer indolization. Employing aryl hydrazines with α-substituents next to the hydrazine group prevents the rearomatization which takes place in common Fischer indole syntheses, thus enabling the hydrolysis of the generated diimine species. In the presence of STRIP as catalyst, a variety of different 1,4-diketones could be obtained in generally high yields, diastereo- and enantioselectivities. The last part of this thesis deals with the development of an organocatalytic asymmetric stereodivergent synthesis of novel 3H- and 2H-pyrroles, applying an interrupted Fischer indolization and for the 2H-pyrroles a subsequent stereospecific [1,5]-alkyl shift. Employing STRIP as catalyst afforded the corresponding products in good to excellent yields and enantioselectivities. Preliminary biological investigations of these novel structure motifs in cell-based assays, monitoring biological signal transduction pathways showed an inhibition of the Hedgehog signaling pathway in a μM range.

Asymmetric polygons with maximum area

We say that a polygon inscribed in the circle is asymmetric if it contains no two antipodal points being the endpoints of a diameter. Given n diameters of a circle and a positive integer k < n, this paper addresses the problem of computing a maximum area asymmetric k-gon having as vertices k < n endpoints of the given diameters. The study of this type of polygons is motivated by ethnomusiciological applications.

Rhodium-catalysed enantioselective C-H functionalization in asymmetric synthesis

Alternating surgeries

This thesis is concerned with the question of when the double branched cover of an alternating knot can arise by Dehn surgery on a knot in S^3. We approach this problem using a surgery obstruction, first developed by Greene, which combines Donaldson's Diagonalization Theorem with the $d$-invariants of Ozsvath and Szabo's Heegaard Floer homology. This obstruction shows that if the double branched cover of an alternating knot or link L arises by surgery on S^3, then for any alternating diagram the lattice associated to the Goeritz matrix takes the form of a changemaker lattice. By analyzing the structure of changemaker lattices, we show that the double branched cover of L arises by non-integer surgery on S^3 if and only if L has an alternating diagram which can be obtained by rational tangle replacement on an almost-alternating diagram of the unknot. When one considers half-integer surgery the resulting tangle replacement is simply a crossing change. This allows us to show that an alternating knot has unknotting number one if and only if it has an unknotting crossing in every alternating diagram. These techniques also produce several other interesting results: they have applications to characterizing slopes of torus knots; they produce a new proof for a theorem of Tsukamoto on the structure of almost-alternating diagrams of the unknot; and they provide several bounds on surgeries producing the double branched covers of alternating knots which are direct generalizations of results previously known for lens space surgeries. Here, a rational number p/q is said to be characterizing slope for K in S^3 if the oriented homeomorphism type of the manifold obtained by p/q-surgery on K determines K uniquely. The thesis begins with an exposition of the changemaker surgery obstruction, giving an amalgamation of results due to Gibbons, Greene and the author. It then gives background material on alternating knots and changemaker lattices. The latter part of the thesis is then taken up with the applications of this theory.

Catalytic asymmetric synthesis of alfa,alfa-disubstituted alfa-thio- and alfa-amino acid derivatives

449 p.

Effects of an asymmetric friction on the nonlinear equilibration of a baroclinic system

Following some recent linear and nonlinear studies the authors examine, using numerical simulations of a classical two-layer model, the effect of an asymmetric friction on the nonlinear equilibrium of moderately unstable baroclinic systems, The results show that the presence of an asymmetric friction leads to a significant wave scale selection: ''long'' waves (in terms of their zonal wavelengths) emerge with a traditional asymmetric friction (with the upper layer less viscous than the lower layer), while only ''short'' waves dominate with a nontraditional asymmetric friction (with the lower layer less viscous than the upper layer). The role of the nonlinear interactions and. more precisely, the effects of an asymmetric friction on the wave-mean flow and wave-wave interactions; and their consequences on the wave scale selection are examined.

Invertibility characterization of Wiener-Hopf plus Hankel operators on variable exponent Lebesgue spaces via even asymmetric factorization

We obtain invertibility and Fredholm criteria for the Wiener-Hopf plus Hankel operators acting between variable exponent Lebesgue spaces on the real line. Such characterizations are obtained via the so-called even asymmetric factorization which is applied to the Fourier symbols of the operators under study.

States' Responding Behavior in Conflict: Asymmetric Response and Strategic Conflict Avoidance

State responses to external threats and aggression are studied with focus on two different rationales: (1) to make credible deterrent threats to avoid being exploited, and (2) to minimize the risk of escalation to unwanted war. Given external aggression, the target state's responding behavior has three possibilities: concession (under-response), reciprocation, and escalation. This study focuses on the first two possibilities and investigates how the strategic nature of crisis interaction can explain the intentional choice of concession or avoidance of retaliation. I build a two-level bargaining model that accounts for the domestic bargaining situation between the leader and the challenger for each state. The model's equilibrium shows that the responding behavior is determined not only by inter-state level variables (e.g. balance of power between two states, or cost of war that each state is supposed to pay), but also the domestic variables of both states. Next, the strategic interaction is rationally explained by the model: as the responding state believes that the initiating state has strong domestic challenges and, hence, the aggression is believed to be initiated for domestic political purposes (a rally-around-the-flag effect), the response tends to decrease. The concession is also predicted if the target state leader has strong bargaining power against her domestic challengers \emph{and} she believes that the initiating leader suffers from weak domestic standing. To test the model's prediction, I conduct a lab experiment and case studies. The experimental result shows that under an incentivized bargaining situation, individual actors are observed to react to hostile action as the model predicts: if the opponent is believed to suffer from internally driven difficulties, the subject will not punish hostile behavior of the other player as severely as she would without such a belief. The experiment also provides supporting evidence for the choice of concession: when the player finds herself in a favorable situation while the other has disadvantages, the player is more likely to make concessions in the controlled dictator game. Two cases are examined to discuss how the model can explain the choice of either reciprocation or concession. From personal interviews and fieldwork in South Korea, I find that South Korea's reciprocating behavior during the 2010 Yeonpyeong Island incident is explained by a combination of `low domestic power of initiating leader (Kim Jong-il)' and `low domestic power of responding leader (Lee Myung-bak).' On the other hand, the case of EC-121 is understood as a non-response or concession outcome. Declassified documents show that Nixon and his key advisors interpreted the attack as a result of North Korea's domestic political instabilities (low domestic power of initiating leader) and that Nixon did not have difficulties at domestic politics during the first few months of his presidency (high domestic power of responding leader).

Alfa'-oxy enones and pyrrolidin-2,3-diones as efficient new templates in asymmetric organocatalytic Michael reactions

470 p.