Supporting Cubane’s Renaissance: Metathesis reactions on 4-iodo-1-vinylcubane and Stetter reaction on 1-iodocubane-4-carboxaldehyde

Cubane is a peculiar cube-shaped alkane molecule with a rigid, regular structure. This makes it a good scaffold, i.e. a molecular platform to which the substituents are arranged in a specific and fixed orientation. Moreover, cubane has a body diagonal of 2.72 Å, very similar to the distance across the benzene ring, i.e. 2.79 Å. Thus, it would be possible to use cubane as a scaffold in medicinal and material chemistry as a benzene isostere 1,2. This could lead to advantages in terms of solubility and toxicity and could provide novel properties. For this purpose, the possibility of performing “modern organic chemistry” on the cubane scaffold has to be studied. This project was entirely carried out in the framework of the Erasmus+ mobility programme at the Trinity College (Dublin, IRL) under the supervision of prof. M. O. Senge. The main goal of this project was to widen the knowledge on cubane chemistry. In particular, it was decided to test reactions that were never applied to the scaffold before, such as metathesis of 4-iodo-1-vinylcubane and Stetter reaction of 1-iodocubane-4-carboxaldehyde. These two molecules were synthesized in 10 and 9 steps respectively from commercially available cyclopentanone, following a known procedure. Unfortunately, metathesis with different olefins, such as styrene, α,β unsaturated compounds and linear α-olefins failed under different conditions, highlighting cubane behaves as a Type IV, challenging olefin under metathesis conditions. Even the employment of a specific catalyst for hindered olefins failed in the cross-coupling with linear α-olefins. On the other hand, two new molecules were synthesized via Stetter reaction and benzoin condensation respectively. Even if the majority of the reactions were not successful, this work can be seen as an inspiration for further investigation on cubane chemistry, as new questions were raised and new opportunities were envisioned.

Typing your mind away. Comparing keylogged tasks with the Task Segment Framework

One of the main process features under study in Cognitive Translation & Interpreting Studies (CTIS) is the chronological unfolding of the tasks. The analyses of time spans in translation have been conceived in two ways: (1) studying those falling between text units of different sizes: words, phrases, sentences, and paragraphs; (2) setting arbitrary time span thresholds to explore where do they fall in the text, whether between text units or not. Writing disfluencies may lead to comprehensive insights into the cognitive activities involved in typing while translating. Indeed, long time spans are often taken as hints that cognitive resources have been subtracted from typing and devoted to other activities, such as planning, evaluating, etc. This exploratory, pilot study combined both approaches to seek potential general tendencies and contrasts in informants’ inferred mental processes when performing different writing tasks, through the analysis of their behaviors, as keylogged. The study tasks were retyping, monolingual free writing, translation, revision and a multimodal task—namely, monolingual text production based on an infographic leaflet. Task logs were chunked, and shorter time spans, including those within words, were analyzed following the Task Segment Framework (Muñoz & Apfelthaler, in press). Finally, time span analysis was combined with the analysis of the texts as to their lexical density, type-token ratio and word frequency. Several previous results were confirmed, and some others were surprising. Time spans in free writing were longer between paragraphs and sentences, possibly hinting at planning and, in translation, between clauses and words, suggesting more cognitive activities at these levels. On the other hand, the infographic was expected to facilitate the writing process, but most time spans were longer than in both free writing and translation. Results of the multimodal task and some other results suggest venues for further research.