Total synthesis of macrosphelide A by way of palladium-catalyzed carbonylative esterification

We achieved the total synthesis of macrosphelide A, as part of a combinatorial library of its analogues. The key intermediate, the seco-acid derivative, was prepared from the corresponding vinyl iodide using sequential carbonylative esterification.     

Highly Active Catalysts for the Transfer Dehydrogenation of Alkanes: Synthesis and Application of Novel 7–6–7 Ring‐Based Pincer Iridium Complexes

A series of Ir–PCP pincer precatalysts [(7–6–7‐^RPCP)Ir(H)(Cl)] and [(7–6–7‐^ArPCP)Ir(H)(Cl)(MeCN)] bearing a novel “7–6–7” fused‐ring skeleton have been synthesized based upon the postulate that the catalytic species would have durability due to their rather rigid structure and high activity owing to the low but sufficient flexibility of their backbones, which are not completely fixed. Treatment of these precatalysts with NaOtBu gave rise to the active 14 electron (14e) species [(7–6–7‐^iPrPCP)Ir] and [(7–6–7‐^PhPCP)Ir], which can trap hydrogen and were spectroscopically characterized as the tetrahydride complexes. Both [(7–6–7‐^iPrPCP)Ir] and [(7–6–7‐^PhPCP)Ir] were found to be highly effective in the transfer dehydrogenation of cyclooctane with tert‐butylethylene as the hydrogen acceptor, the initial reaction rate at high temperature (230 °C) being higher for [(7–6–7‐^iPrPCP)Ir] than [(7–6–7‐^PhPCP)Ir], and the turnover number (TON) of the overall hydrogen transfer being higher for the latter. Nonetheless, the estimated TONs were as high as 4600 and 4820 for the two complexes at this temperature, respectively, which are unprecedented absolute values. In terms of durability, the [(7–6–7‐^PhPCP)Ir] complex is the catalyst of choice for this reaction. Structural analysis and computational studies support the importance of the low flexibility of the ligand core.     

Cost-effective production policy for a stochastic unreliable manufacturing system

^** Email: dohi{at}rel.hiroshima-u.ac.jp The paper deals with an economic manufacturing quantity (EMQ)problem for an unreliable manufacturing system in both continuous-and discrete-time settings. The time to machine failure andcorrective and preventive repair times of the production facilityare assumed to follow arbitrary probability distributions. Thetraditional method of determining the EMQ policy for a failure-pronemanufacturing system is based on the minimization of the long-runaverage cost in the steady state. In this paper, an alternativecriterion of optimality called cost effectiveness is introduced.The criteria for the existence and uniqueness of the optimalproduction time maximizing the cost effectiveness are derivedanalytically under general failure and specific repair (correctiveand preventive) time distributions. The optimal cost-effectiveand average cost production policies are numerically calculatedand compared in terms of their performances.     

A new methodology for the synthesis of fluorinated exo-glycals and their time-dependent inhibition of UDP-galactopyranose mutase

Fluorinated carbohydrates constitute a very important class of mechanistic probes for glycosyl-processing enzymes. In this study, we describe the first synthesis of fluorinated and phosphonylated exo-glycals and their corresponding nucleotide sugars in the galactofuranose series. The synthetic protocol that we have developed is a Selectfluor-mediated fluorination/elimination sequence on phosphonylated exo-glycals, and it offers a new entry into fluorinated carbohydrate chemistry. The challenging E/Z stereochemical assignment of the resulting tetrasubstituted alkenes, which bear an alkoxy, an alkyl, a fluoro, and a phosphonyl group, has been achieved through NMR experiments. The corresponding (E)- and (Z)-nucleotide fluorosugars have been prepared and tested as inhibitors of UDP-galactopyranose mutase (UGM). UGM is a flavoenzyme that catalyzes the isomerization of uridine diphosphate(UDP)-galactopyranose into UDP-galactofuranose, a key step of the biosynthesis of important mycobacterial cell-wall glycoconjugates. The two diastereomeric molecules were found to display time-dependent inactivation of UGM, as expected from preliminary results using non-fluorinated exo-glycal nucleotides. The inhibitory properties of the two fluorinated molecules led us to suggest that the inactivation mechanism proceeds through two-electron processes, despite the presence of the flavin cofactor within the UGM catalytic site.     

Universal extra dimensions on real projective plane

We propose a six-dimensional Universal Extra Dimensions (UED) model compactified on a real projective plane RP²${\mathit{RP}}^2$, a two-sphere with its antipodal points being identified. We utilize the Randjbar-Daemi–Salam–Strathdee spontaneous sphere compactification with a monopole configuration of an extra UX₍₁₎$U{(1)}_X$ gauge field that leads to a spontaneous radius stabilization. Unlike the sphere and the S²/Z₂$S^2/Z_2$ orbifold compactifications, the massless UX₍₁₎$U{(1)}_X$ gauge boson is safely projected out. We show how a compactification on a non-orientable manifold results in a chiral four-dimensional gauge theory by utilizing 6D chiral gauge and Yukawa interactions. The resultant Kaluza–Klein mass spectra are distinct from the ordinary UED models compactified on torus. We briefly comment on the anomaly cancellation and also on a possible dark matter candidate in our model.