Oxidation of diazenyl-protected N-heterocycles - a new entry to functionalized lactams

Functionalized lactams are an important class of heterocycles since they are useful intermediates in organic synthesis and show biological activity in diverse therapeutic applications. In the herein presented study, a strategy for the synthesis of N-aryldiazenyllactams, offering the direct access to protected lactam derivatives is described. After the formation of triazenes from diazonium salts and commercially available N-heterocycles, oxidation (directed CH activation) with periodate under ruthenium catalysis furnished N-diazenyllactams in one step. To demonstrate the suitability of the resulting lactams for further functionalizations, the alkylation of a N-diazenyllactam is presented for one example.Peer reviewe

Synthesis of Indenes by Tandem Gold(I)-Catalyzed Claisen Rearrangement/Hydroarylation Reaction of Propargyl Vinyl Ethers

The tandem gold(I)-catalyzed propargyl Claisen rearrangement/hydroarylation reaction of suitable propargyl vinyl ethers, followed by in situ reduction of the resulting carbonyl group, provides functionalized indenes in good to excellent yields. The reaction occurs at room temperature in dichloromethane in the presence of 3 mol % [IPrAuCl]/AgBF4 as the best catalytic system. With phosphine ligands no cyclization of the allene intermediate instead occurs. A variety of substituents and functional groups present on the substrate are tolerated. The effect of the aryl ring substituents and the results of a DFT computational study suggest that the final hydroarylation is the rate determining step of this cascade process. Further in situ chain elongation, prior final work up of the tandem process, can be carried out by Wittig olefination of the aldehyde functionality, thus incrementing the diversity of the products obtainedFinancial support from University of Florence is acknowledged. Dr Alessandro Pratesi and Dr Susanna Pucci are acknowledged for technical assistance. Ente Cassa di Risparmio di Firenze is acknowledged for granting a 400 MHz NMR instrument. G.Z. and E.G.-B. thank the European Funding Horizon 2020-MSCA (ITN-EJD CATMEC 14/06-721223) and also SGiker (UPV/EHU) for human and technical support

Towards the realisation of a fully integrated Interactive Computer Music System (ICMS), adopting Transformative Expressive Dimensions

The principal aim of conducting this research project is to advance the field of human-computer interaction (HCI) in music through the inception of new and exciting ideas relating to the conceptual and aesthetic values and characteristics associated with interactive computer music system (ICMS) design, development and implementation. This exploratory investigation has been carried out through the continued development of a unique screen-based ICMS, ScreenPlay, which brings together aspects of many prominent, pre-existing system design models along with other novel inclusions, such as the capability of operating as both a multi-user-and-computer collaborative, improvisatory interactive performance system and a single-user-and-computer studio compositional tool for Ableton Live, and the implementation of Markovian generative and topic-theory-inspired transformative algorithms to provide new ways of breaking routine in collaborative improvisation and generating new musical ideas in composition, as well as providing new dimensions of expressivity. The intention being that the culmination of these efforts should be the establishment of a system design model that offers the user(s)/performer(s) a significantly more engaging, intuitive and complete interactive musical experience than that afforded by any currently available system. This is not an objective that should be perceived as being born of arrogance or ignorance; many established and commercially successful ICMSs provide users with amazing and unique experiences, and the value of their contribution to the field of HCI in music is not to be underestimated or taken for granted. However, for all the relative strengths and possibilities of interacting with these systems, there is potential for improvement and evolution in equal measure. This is largely due to the tendency of ICMS developers to focus (sometimes almost exclusively) on providing the best possible experience when engaging with a system only with regard to a single parameter/characteristic of the musical output at the expense of providing depth-in-control at any level over some or any of the many other parameters/characteristics available. It is necessary for all forms of technology and art to continually improve and evolve beyond what has already been achieved in order to avoid extinction, and nowhere is this more apparent than within an innovative and niche field of research such as HCI in music