Mechanistic analysis of an asymmetric palladium-catalyzed conjugate addition of arylboronic acids to β-substituted cyclic enones.

An asymmetric palladium-catalyzed conjugate addition reaction of arylboronic acids to enone substrates was investigated mechanistically. Desorption electrospray ionization coupled to mass spectrometry was used to identify intermediates of the catalytic cycle and delineate differences in substrate reactivity. Our findings provide evidence for the catalytic cycle proceeding through formation of an arylpalladium(II) cation, subsequent formation of an arylpalladium-enone complex, and, ultimately, formation of the new C-C bond. Reaction monitoring in both positive and negative ion modes revealed that 4-iodophenylboronic acid formed a relatively stable trimeric species under the reaction conditions

The urban bioeconomy: extracting value from the ecological and biophysical

Cities have tended to be seen as net consumers of ecological goods and exporters of ecological bads. However, over recent years urban metabolism, circular economy and bioeconomy concepts have sought to rebalance this seemingly parasitical relationship by seeing the urban as an ecological resource to be exploited for profit. In this review paper, we investigate the ways in which the assets and metabolic flows of the city are being recharacterised as a source of value to be maintained, extracted, enhanced and exploited. Our approach is twofold. First, we examine areas of latent potential for urban bioeconomic exploitation and issues raised in terms of fair and just cities. Second, we examine issues, tensions and challenges in reimagining the city as a site of bioeconomic value. The paper makes a distinctive contribution to the literature by defining and critically analysing the new urban bioeconomy as a form of environmental value creation

Localizing the SDGs in England: challenges and value propositions for local government

The United Nations' Development Goals (SDGs) have been criticized but are nonetheless seen by many as an important, if imperfect, international effort to address climate and environmental change, resource depletion and the unsustainability of contemporary life. Many of the Goals need to be implemented at the local level, yet sub-national governments have not been granted any enhanced status at the UN to facilitate this process. As a result, the role and effectiveness of local governments in localizing the SDGs is dependent on multi-level arrangements within respective national contexts. In this paper we present findings on the challenges facing local authorities in England, namely co-dependent ambivalence, partial holism and narrow practices of knowledge governance. We draw on work carried out collaboratively with local authorities and other stakeholders in Greater Manchester and Sheffield, and a UK-wide national workshop. These challenges explain the relatively low uptake and engagement with the SDGs in the context of wider political and economic concerns compared with international comparator cities. Against this background our research found that making the Goals real, relevant, relatable and relational offered a tactical route to localization for English local government

Z-Selective Cross-Metathesis and Homodimerization of 3E-1,3-Dienes: Reaction Optimization, Computational Analysis, and Synthetic Applications

Olefin metathesis reactions with 3E-1,3-dienes using Z-selective cyclometalated ruthenium benzylidene catalysts are described. In particular, a procedure for employing 3E-1,3-dienes in Z-selective homodimerization and cross-metathesis with terminal alkenes is detailed. The reaction takes advantage of the pronounced chemoselectivity of a recently reported ruthenium-based catalyst containing a cyclometalated NHC ligand for terminal alkenes in the presence of internal E-alkenes. A wide array of commonly encountered functional groups can be tolerated, and only a small excess (1.5 equiv) of the diene coupling partner is required to achieve high yields of the desired internal E,Z-diene cross-metathesis product. Computational studies have been performed to elucidate the reaction mechanism. The computations are consistent with a diene-first pathway. The reaction can be used to quickly assemble structurally complex targets. The power of this cross-metathesis reaction is demonstrated by the concise syntheses of two insect pheromones

An unexpected Ireland–Claisen rearrangement cascade during the synthesis of the tricyclic core of Curcusone C: Mechanistic elucidation by trial-and-error and automatic artificial force-induced reaction (AFIR) computations

In the course of a total synthesis effort directed toward the natural product curcusone C, the Stoltz group discovered an unexpected thermal rearrangement of a divinylcyclopropane to the product of a formal Cope/1,3-sigmatropic shift sequence. Since the involvement of a thermally forbidden 1,3-shift seemed unlikely, theoretical studies involving two approaches, the “trial-and-error” testing of various conceivable mechanisms (Houk group) and an “automatic” approach using the Maeda–Morokuma AFIR method (Morokuma group) were applied to explore the mechanism. Eventually, both approaches converged on a cascade mechanism shown to have some partial literature precedent: Cope rearrangement/1,5-sigmatropic silyl shift/Claisen rearrangement/retro-Claisen rearrangement/1,5-sigmatropic silyl shift, comprising a quintet of five sequential thermally allowed pericyclic rearrangements

A Longitudinal Analysis of Moving Desires, Expectations and Actual Moving Behaviour

Residential mobility theory proposes that moves are often preceded by the expression of moving desires and expectations. Much research has investigated how individuals form these premove thoughts, with a largely separate literature examining actual mobility. Although a growing number of studies link premove thoughts to subsequent moving behaviour, these often do not distinguish explicitly between different types and combinations of premove thoughts. Using 1998–2006 British Household Panel Survey data, this study investigates whether moving desires and expectations are empirically distinct premove thoughts. Using multinomial regression models we demonstrate that moving desires and expectations have different meanings, and are often held in combination: the factors associated with expecting to move differ depending upon whether the move is also desired (and vice versa). Next, using panel logistic regression models, we show that different desire–expectation combinations have different effects on the probability of subsequent moving behaviour. The study identified two important groups generally overlooked in the literature: those who expect undesired moves and those who desire to move without expecting this to happen.The definitive, peer reviewed and edited version of this article is published in Environment and Planning A, 2011, 43(11), pp. 2742-2760, doi:10.1068/a44105

Molecular robots guided by prescriptive landscapes

Traditional robots rely for their function on computing, to store internal representations of their goals and environment and to coordinate sensing and any actuation of components required in response. Moving robotics to the single-molecule level is possible in principle, but requires facing the limited ability of individual molecules to store complex information and programs. One strategy to overcome this problem is to use systems that can obtain complex behaviour from the interaction of simple robots with their environment. A first step in this direction was the development of DNA walkers, which have developed from being non-autonomous, to being capable of directed but brief motion on one-dimensional tracks. Here we demonstrate that previously developed random walkers—so-called molecular spiders that comprise a streptavidin molecule as an inert ‘body’ and three deoxyribozymes as catalytic ‘legs’—show elementary robotic behaviour when interacting with a precisely defined environment. Single-molecule microscopy observations confirm that such walkers achieve directional movement by sensing and modifying tracks of substrate molecules laid out on a two-dimensional DNA origami landscape. When using appropriately designed DNA origami, the molecular spiders autonomously carry out sequences of actions such as ‘start’, ‘follow’, ‘turn’ and ‘stop’. We anticipate that this strategy will result in more complex robotic behaviour at the molecular level if additional control mechanisms are incorporated. One example might be interactions between multiple molecular robots leading to collective behaviour; another might be the ability to read and transform secondary cues on the DNA origami landscape as a means of implementing Turing-universal algorithmic behaviour

Z-to-E isomerization processes in reactions catalyzed by cyclometalated ruthenium alkylidenes

The Z-content of products generated in reactions catalyzed by adamantyl-activated Z-selective metathesis catalysts is at first very high but degrades at higher conversions. The degree to which this undesirable process occurs is dependent on both the substrate and catalyst structure. Studies of Z-to-E isomerization processes and methods of preventing them are explored. Furthermore, an interesting Fischer carbene species was found to affect these isomerization processes

Metathesis and Decomposition of Fischer Carbenes of Cyclometalated Z-Selective Ruthenium Metathesis Catalysts

The addition of vinyl ethers to Z-selective, cyclometalated ruthenium metathesis catalysts generates Fischer carbene complexes. Although Fischer carbenes are usually thought to be metathesis inactive, we show that Fischer carbenes are metathesis active under certain circumstances. These species were found to decompose facilely to Ru hydride complexes, as identified by both experiment and computation. Since vinyl ethers are often used to quench metathesis reactions implementing Ru-based metathesis catalysts, their decomposition to hydrides can have a deleterious effect on the desired stereochemistry of the olefin product