Synthesis based on cyclohexadienes Part 36: an efficient methodology for the construction of spiro[4.5]decanes: a formal synthesis of acorone

An efficient strategy for the contruction of spiro[4.5] decanes is described and involves a bridgehead substitution of a methoxyl group by a methyl group followed by an oxidative cleavage of the tricyclo[5.2.2.0(1,5)] undecane 25 to produce the spiro[4.5] decanes 31 & 32 which are intermediates in the synthesis of acorone. A novel one-pot conversion of alpha-methoxy carboxylic acid to alpha-methyl carboxylic acid is described.

Enantioselective Formal Synthesis of Palmerolide A

Enantioselective formal synthesis of macrolactone palmerolide A, a polyketide marine natural product, is described. Key strategies in the synthesis include the oxidative furan ring-opening of a chiral furyl carbinol for the installation of the 1,4-dienol core and a Jung nonaldol-aldol reaction for the dienamide core.

Towards formal verification of analog mixed signal designs using SPICE circuit simulation traces

An extension to a formal verification approach of hybrid systems is proposed to verify analog and mixed signal (AMS) designs. AMS designs can be formally modeled as hybrid systems and therefore lend themselves to the formal analysis and verification techniques applied to hybrid systems. The proposed approach employs simulation traces obtained from an actual design implementation of AMS circuit blocks (for example, in the form of SPICE netlists) to carry out formal analysis and verification. This enables the same platform used for formally validating an abstract model of an AMS design, to be also used for validating its different refinements and design implementation; thereby, providing a simple route to formal verification at different levels of implementation. The feasibility of the proposed approach is demonstrated with a case study based on a tunnel diode oscillator. Since the device characteristic of a tunnel diode is highly non-linear with a negative resistance region, dynamic behavior of circuits in which it is employed as an element is difficult to model, analyze and verify within a general hybrid system formal verification tool. In the case study presented the formal model and the proposed computational techniques have been incorporated into CheckMate, a formal verification tool based on MATLAB and Simulink-Stateflow Framework from MathWorks.

An Enantiospecific Formal Total Synthesis of the 5-8-5 Tricyclic Diterpene ent-Fusicoauritone

An enantiospecific formal total synthesis of the 5-8-5 tricyclic diterpene fusicoauritone has been accomplished, starting from 5-isopropyl-2-methylcyclopent-1-enemethanol [available in three steps from (R)-dihydrolimonene] employing two ring-closing-metathesis reactions for the construction of the eight- and five-membered rings.

Formal Synthesis of Actin Binding Macrolide Rhizopodin

Formal synthesis, of an actin binding macrolide rhizopodin was achieved in 19 longest linear steps. The key features of the synthesis include a stereoselective Mukaiyama aldol reaction, dual role of a Nagao auxiliary (first, as a chiral auxiliary of choice for installing hydroxy centers and, later, as an acylating agent to form an amide bond with an amino alcohol), late stage oxazole formation, and Stille coupling reactions.

Unexpected mechanism for formal 2+2] cycloadditions of metallacyclocumulenes

The formation of radialene complex 6M proceeds through a three-membered metallacyclopropene complex 7M, contrary to the prevailing notion of simple dimerization of metallacyclocumulene 1M. The 1M-7M equilibrium, which is predominantly governed by the size-dependent ligand binding of the metal atoms, plays a decisive role in the chemistry of Cp2M-ligand complexes. This size dependency is further fine-tuned by the substituents on the substrates and helps in exploiting these classes of metallacycles to generate new chemistry.

Enantiospecific Formal Total Synthesis of Iriomoteolide 3a

A formal total synthesis of the marine macrolide iriomoteolide3a is described. Salient features of the synthesis include the elaboration of a -keto phosphonate derived from D-(-)-tartaric acid and the extension of a chiral butyrolactone derived from L-glutamic acid. Ring-closing metathesis is employed to construct the macrolactone core of the natural product.

Using formal reasoning on a model of tasks for FreeRTOS

FreeRTOS is an open-source real-time microkernel that has a wide community of users. We present the formal specification of the behaviour of the task part of FreeRTOS that deals with the creation, management, and scheduling of tasks using priority-based preemption. Our model is written in the Z notation, and we verify its consistency using the Z/Eves theorem prover. This includes a precise statement of the preconditions for all API commands. This task model forms the basis for three dimensions of further work: (a) the modelling of the rest of the behaviour of queues, time, mutex, and interrupts in FreeRTOS; (b) refinement of the models to code to produce a verified implementation; and (c) extension of the behaviour of FreeRTOS to multi-core architectures. We propose all three dimensions as benchmark challenge problems for Hoare's Verified Software Initiative.

Organocatalytic Enantioselective Formal C(sp(2))-H Alkylation

An organocatalytic enantioselective formal C(sp(2))-H alkylation is reported. This alkylative desymmetrization of prochiral 2,2-disubstituted cyclopentene-1,3-dione is catalyzed by a bifunctional tertiary aminourea derivative, utilizes air-stable and inexpensive nitroalkanes as the alkylating agents, and delivers synthetically versatile five-membered carbocycles containing an all-carbon quaternary stereogenic center remote from the reaction site in excellent enantioselectivity.

A versatile, RCM based approach to eudesmane and dihydroagarofuran sesquiterpenoids from (-)-carvone: a formal synthesis of (-)-isocelorbicol

An enantiospecific and diversity oriented approach to a range of functionalized eudesmane, nor-, iso-, and dihydroagarofuran frameworks from (-)-carvone is delineated. The cornerstone of this approach is the installation of the quaternary carbon center through reductive opening of the carvone epoxide and setting-up of RCM reaction to generate the bicyclic eudesmane framework. Various options like carbocation mediated oxycyclization and intramolecular hydroxy directed epoxide opening have been explored for the construction of the bridged tetrahydrofuran moiety. Among the several eudesmane and dihydroagarofurans accessed during the present study, one has been previously elaborated to iso-celorbicol, thus constituting its formal synthesis. (C) 2015 Elsevier Ltd. All rights reserved.

Formal synthesis of degraded sterol (+)-aplykurodinone-1

The formal synthesis of aplykurodinone-1 is accomplished starting from a suitably functionalized bicyclic lactone having the requisite cis-fused ring junction with a quaternary chiral center that was assembled following a Cp2TiCl-mediated radical cyclization protocol. Our synthetic route further elaborates implementation of Grubbs ring closing metathesis (RCM), Eschenmoser-Claisen rearrangement and iodo-lactonization reactions for the synthesis of the final tricyclic precursor of the target molecule. (C) 2015 Elsevier Ltd. All rights reserved.

Lineamientos para un programa de Educación ambiental no formal para el Barrio "El Rodeo", Distrito VI, Managua

El estudio fue desarrollado en el año 2003 para definir los lineamientos para un Programa de Educación Ambiental No Formal, los cuales serán desarrollados con base en las características socio-educativas de las comunidades y en los conflictos ambientales del Barrio El Rodeo, Distrito VI, Managua. Los problemas socio-ambientales existentes en el barrio El Rodeo están relacionados con: tasa alta de desempleo, ingreso familiar promedio bajo, afecciones por enfermedades del sistema respiratorio, acceso limitado de agua potable en los negocios que preparan y comercializan alimentos, inexistencia de sistema de alcantarillado sanitario, calles sin pavimentar, contaminación del aire por emisiones vehiculares, contaminación del agua por vertidos industriales y contaminación por desechos sólidos. Aunque esta situación es evidente y conocida por la sociedad civil y los decisores políticos, se han realizado muy pocas acciones de gestión ambiental para atenderla. La propuesta de lineamientos para un Programa de Educación Ambiental No Formal está dirigida a contribuir a la solución de los conflictos ambientales del barrio El Rodeo. Su implementación contribuiría a la protección y conservación ambiental, con el fin de generar beneficios a las personas que habitan este barrio urbano-marginal de Managua.

El objeto formal de la vis cogitativa en Santo Tomás de Aquino

Resumen: De acuerdo a la mente de Santo Tomás de Aquino, la potencia de conocimiento sensible que se denomina «cogitativa » es susceptible de una doble consideración. Por un lado, es la estimativa animal y, como tal, aprehende su mismo objeto formal quod, esto es, las intenciones de beneficio o perjuicio a nivel sensible. Pero a causa de su particular modo de operar, esas intenciones no son conocidas por ella solamente en orden a la conservación del individuo humano o de la especie a la que él pertenece. El reconocimiento de una doble dimensión de la cogitativa está en Santo Tomás justificado por la particular relación que existe entre ella y la razón universal. Por un lado, la cogitativa no es una facultad distinta de la estimativa natural. Por esto, ella aprehende las intenciones necesarias para la perfección de la vida sensitiva humana. Por otro lado, la razón ejerce sobre la cogitativa un influjo particular que la hace operar a su modo, esto es, de manera discursiva. Este carácter móvil en la aprehensión de la cogitativa permite la conformación de una experiencia a nivel sensible, en virtud de la cual su objeto formal se ve ampliado. Esto resulta aún más razonable si se tiene en cuenta que el conocimiento sensorial del hombre prepara el intelectual. De esta manera, la cogitativa no aprehende simplemente al individuo como beneficioso o perjudicial para la subsistencia del cognoscente, sino como sujeto de una cierta naturaleza.

La abstracción formal y la validación del razonamiento inductivo

Resumen: Suele admitirse que uno de los problemas pendientes, al menos desde Hume, en la teoría de la ciencia es la justificación crítica de los procesos inductivos, que son los que siguen las ciencias experimentales, como son las ciencias naturales. Frente a las ineficaces explicaciones aportadas por el empirismo o neopositivismo, así como por los racionalismos o idealismos, que son radicalmente incapaces para resolver el problema, nosotros presentamos la respuesta del realismo aristotélico, basada en el correcto concepto de abstracción formal, ignorado o malentendido incluso por muchos aristotélicos tanto antiguos como modernos. La respuesta consiste, en suma, en ver que el término del proceso inductivo, en cuanto llega a conclusiones universales a partir de lo particular, debe estar mediado por un proceso previo de abstracción de la forma, bien entendida, en lo mismo concreto y particular. Ello permite ver que la conclusión universal no desborda las premisas, que es el problema clásico de la epagogé aristotélica.