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Selective incorporation of deuterium atoms into molecules is of high interest for labeling purposes and for optimizing properties of drug candidates. A mild and environmentally benign method for the deuteration of alkyl iodides via radical pathway using D2O as source of deuterium has been developed. The reaction is initiated and mediated by triethylborane in the presence of dodecanethiol as a catalyst. This method is compatible with a wide range of functional groups and provides the monodeuterated products in good yields and with a high level of deuterium incorporation. It opens promising opportunities for the development of enantioselective radical reactions. Moreover, a revision of the mechanism of the deoxygenation reaction of xanthates using R3B and water (Wood deoxygenation) is presented.

Roman Polanski ha espresso una particolare sensibilita per le "atmosfere paranoiche" ed e un grande maestro del cosiddetto thriller psicoanalitico sin dal film Repulsion del 1965, ma soprattutto ne L’inquilino del terzo piano (1976). Il cinema rende mirabilmente il senso di estraneita dell’esistenza grazie alla sua capacita di mettere in evidenza particolari in apparenza irrilevanti, ma tali da comunicare un sottile disagio. Il regista esplora anche il rapporto fra paranormale e paranoia nel film Rosemary’s Baby (1968); d’altra parte anche Stanley Kubrick nel suo capolavoro Shining esplora questo stesso tema. Il tema dello sdoppiamento della personalita compare in film quali Fight Club (1999) e Lenny (1974), ma assume un aspetto ancor piu visionario e "distopico" in Videodrome (1983) e eXistenz (1999) entrambi del regista canadese David Cronenberg. Il tema della paranoia si accompagna ai temi cari alla letteratura fantascientifica in film quali: L’invasione degli ultracorpi (1956), 2001: Odissea nello spazio (1968), Brazil (1985), Gattaca (1997) e Matrix (1999) nei quali e adombrato spesso il tema del rapporto fra dittatura e liberta.

Il disturbo paranoico e quello piu frequentemente rappresentato nel cinema sin dai primi anni del ’900 partendo dal film di Pabst I misteri di un’anima (1926). Lo stesso Libro Rosso di Jung puo essere visto come lo sviluppo di una pre-visione paranoica. Facendo ricorso a spunti clinici e descrivendo esperienze professionali e personali, l’autore indaga il mondo del paranoico attraverso la lettura di alcune memorabili scene cinematografiche. La descrizione di specifici artifici scenografici e di diverse soluzioni cinematografiche da parte dei registi descritti contribuisce alla individuazione di alcuni temi centrali della rappresentazione paranoica dellla realta. Attraverso spunti clinici e racconti sia professinali che personali, l’autore delinea un excursus cinematografico sul tema della paranoia a partire dai primi decenni del secolo scorso fino alla fine degli anni ’90. Vengono presi in esame infatti alcuni film che riescono a rendere il mondo del paranoico nel suo interno vissuto (A Beautiful Mind) ed anche i rapporti fra paranoia e thriller sia di tipo poliziesco (Hitchcock) che psicoanalitico (Polanski e Bunuel).

The aim of this paper is to compare energy consumptions, CO2 emissions, and operative costs of condensing boilers, electric vapour compression heat pumps and gas driven absorption heat pumps to provide space heating and domestic hot water. The analysis is performed for 140 m2 single-family houses in five different Italian cities whose envelope features depend on the location. For each location, two different envelope conditions are considered. The first one is a non-insulated building, while the second one is the same building, but an external thermal insulation is added on vertical walls and roof. To avoid internal renovation, radiators are maintained as emission system. Combined dynamic simulations are performed to appreciate building and system interactions. A 6 second time step is set to evaluate properly interactions and the DHW profile demand. In addition, the GHP dynamic model is a grey box model experimentally validated. The results show that electric vapour compression heat pumps reach the highest non-renewable primary energy savings (>32%) compared to condensing boilers, but their operative costs are higher due to the higher specific cost of electricity in Italy. Gas driven absorption heat pumps achieve a lower consumption reduction than electric heat pumps (>22%), but they have also the minimum operative cost among the three technologies.

Selective incorporation of deuterium atoms into molecules is of high interest for labeling purposes and for optimizing properties of drug candidates. A mild and environmentally benign method for the deuteration of alkyl iodides via radical pathway using D

A general strategy for the synthesis of aignopsanes, a new family of sesquiterpene natural products of marine origin, is presented. The total synthesis of (+)-aignopsanoic acid A (1), (-)-methyl aignopsanoate A (2), and (-)-isoaignopsanoic A (3) has been achieved and their absolute configuration confirmed. (+)-Microcionin-1 (4), a structurally related furanosesquiterpene isolated in both enantiomeric forms from marine sponges, was also synthesized and its absolute configuration established in an unambiguous way. Interestingly, we report that (+)-microcionin-1 (4), can be converted by a simple oxidation process to aignopsanoic acid A (1). This transformation supports the hypothesis that (+)-microcionin-1 (4) may be an intermediate in the biosynthesis of aignopsanes.

The synthesis of an enantiopure building-block with a contiguous all-cis-trimethyldecalin motif embedded in unusual terpenes is described. Starting from the Wieland–Miescher ketone, the key step is a one-pot hydroboration of an exocyclic methylene double bond promoted by disiamylborane and radical-mediated protonolysis of the corresponding alkylborane using 4-tert-butylcatechol.

Il cortometraggio Passing Hearts di J. Brisinger (Sve. 2012) esemplifica perfettamente lo sviluppo dell’"arco narrativo" poiche in soli quindici minuti colpisce al cuore lo spettatore. Infatti sin dai primi istanti crea una aspettativa, delinea uno sviluppo (viaggio) e fa tornare tutti pezzi del puzzle nello splendido finale. Passing Hearts e un cortometraggio emozionante che induce lo spettatore a prendere parte al processo di elaborazione della dolorosa condizione di finitezza umana del protagonista. Il viaggio di Daniel, alla ricerca dei genitori del ragazzo che gli ha donato un cuore, diviene cosi metafora della possibilita di incontro tra esseri umani, dove il corpo, con le sue carenze e i suoi limiti, diviene il mezzo attraverso il quale prendere contatto con la propria ed altrui individualita. Il tema scelto e psicologicamente e filosoficamente rilevante perche riguarda l’emergenza dell’Ombra che assume la forma del doppio, della elaborazione del lutto e della nostra comune fragilita umana.

We disclose a protocol for the palladium-catalyzed ortho-selective C-H deuteration of arenes. Phenylacetic acids and benzoic acids are suitable substrates for this reaction. This reaction offers a catalytic route to ortho-deuterated phenylacetic acids and benzoic acids and demonstrates the sharp difference in reactivity of palladacycle intermediates held together by weak and strong coordination.

A protocol for the Pd(II)-catalyzed ortho-C–H alkylation of phenylacetic and benzoic acids using alkylboron reagents is disclosed. Mono-protected amino acid ligands (MPAA) were found to significantly promote reactivity. Both potassium alkyltrifluoroborates and alkylboronic acids were compatible coupling partners. The possibility of a radical alkyl transfer to Pd(II) was also investigated.

A protocol for the Pd(II)-catalyzed ortho-C—H alkylation of phenylacetic and benzoic acids using alkylboron reagents is disclosed.

Mechanistic investigations on the previously reported reduction of B-alkylcatecholboranes in the presence of methanol led to the disclosure of a new mechanism involving catechol as a reducing agent. More than just revising the mechanism of this reaction, we disclose here the surprising role of catechol, a chain breaking antioxidant, which becomes a source of hydrogen atoms in an efficient radical chain process.

The conversion of alkylboranes to the corresponding alkanes is classically per-formed via protonolysis of alkylboranes. This simple reaction requires the use of severe reaction conditions, that is, treatment with a carboxylic acid at high temperature (150 °C). We report here a mild radical procedure for the transformation of organoboranes to alkanes. 4-tert-Butylcatechol, a well-established radical inhibitor and antioxidant, is acting as a source of hydrogen atoms. An efficient chain reaction is observed due to the exceptional reactivity of phenoxyl radicals toward alkylboranes. The reaction has been applied to a wide range of organoboron derivatives such as B-alkylcatecholboranes, trialkylboranes, pinacolboronates, and alkylboronic acids. Furthermore, the so far elusive rate constants for the hydrogen transfer between secondary alkyl radical and catechol derivatives have been experimentally determined. Interestingly, they are less than 1 order of magnitude slower than that of tin hydride at 80 °C, making catechols particularly attractive for a wide range of transformations involving C-C bond formation.