Enantioselective Intramolecular Michael Addition of Nitronates onto Conjugated Esters: Access to Cyclic γ-Amino Acids with up to Three Stereocenters

A highly stereoselective synthesis of conformationally constrained cyclic γ-amino acids has been devised. The key step involves an intramolecular cyclization of a nitronate onto a conjugated ester, promoted by a bifunctional thiourea catalyst. This methodology has been successfully applied to generate a variety of γ-amino acids, including some containing three contiguous stereocenters, with very high diastereoselectivity and excellent enantioselectivity. It is postulated that an interaction that is key to the success of the process is the simultaneous coordination of the thiourea functionality to both the conjugated ester and the nitronate. Finally, the synthetic utility of these compounds is demonstrated in the synthesis of two dipeptides derived from the C- and N-termini.

Investigations on the effect of amino acids on acrylamide, pyrazines, and Michael addition products in model systems

Acrylamide and pyrazine formation, as influenced by the incorporation of different amino acids, was investigated in sealed low-moisture asparagine-glucose model systems. Added amino acids, with the exception of glycine and cysteine and at an equimolar concentration to asparagine, increased the rate of acrylamide formation. The strong correlation between the unsubstituted pyrazine and acrylamide suggests the promotion of the formation of Maillard reaction intermediates, and in particular glyoxal, as the determining mode of-action. At increased amino acid concentrations, diverse effects were observed. The initial rates of acrylamide formation remained high for valine, alanine, phenylalanine, tryptophan, glutamine, and Ieucine, while a significant mitigating effect, as evident from the acrylamide yields after 60 min of heating at 160 degrees C, was observed for proline, tryptophan, glycine, and cysteine. The secondary amine containing amino acids, proline and tryptophan, had the most profound mitigating effect on acrylamide after 60 min of heating. The relative importance of the competing effect of added amino acids for alpha-dicarbonyls and acrylamide-amino, acid alkylation reactions is discussed and accompanied by data on the relative formation rates of selected amino acid-AA adducts.

A homo-proline tetrazole as an improved organocatalyst for the asymmetric Michael addition of carbonyl compounds to nitro-olefins

A new homo-proline tetrazole derivative 7 has been prepared and shown to have improved properties for achieving asymmetric Michael addition of carbonyl compounds to nitro-olefins.

Organocatalysis with proline derivatives: improved catalysts for the asymmetric Mannich, nitro-Michael and aldol reactions

Tetrazole and acylsulfonamide organocatalysts derived from proline have been synthesised and applied to the asymmetric Mannich, nitro-Michael and aldol reactions to give results that are superior to the proline-catalysed counterpart.

Sleepwalking certainties: agency, aesthetics, and incapacity in W.G. Sebald’s 'Austerlitz' and Hermann Broch’s 'The Sleepwalkers'

When we first encounter the narrator of Austerlitz, he is wandering around the unfamiliar town of Antwerp with, he tells us, “unsicheren Schritten” (1; 9). As well as reflecting the unfamiliarity of the locale, these “uncertain steps” evince a proud modesty characteristic of the classic Sebaldian narrator, a wanderer who discreetly relays the stories of the people and places he is privileged to encounter. Although Sebald does not use the phrase, steps of this sort, unpurposed yet unerring, are made with what is commonly known in German as somnambule Sicherheit: the legendary surefootedness of the sleepwalker. The convergence of sleepwalking and certainty in a single phrase poses an interesting challenge to one of the central tenets of the English-language canonization of Sebald, for his writing has been most highly valued for its ability to move the reader through apparent certainties towards a salutary uncertainty. But somnambule Sicherheit also presents the possibility that the current may be reversed, that narrative may move under cover of uncertainty towards certainty. That Sebald criticism has not been more troubled by this possibility is in no small part due to the fact that it tends to deploy the notion of sleepwalking with a minimum of reflection on its theoretical ramifications. To evoke some of the complexities of this matter, I first offer a brief cultural history of sleepwalking, as well as a brief account of the topic of uncertainty in Sebald criticism. Most of my argument, however, involves an extended comparative analysis of sleepwalking in Sebald's Austerlitz and Hermann Broch's 1933 trilogy The Sleepwalkers. Although these writers have not previously been the object of any sustained comparison, sleepwalking in Broch's novels illuminates much that is left implicit on the topic in Sebald's fiction and points toward some difficult questions regarding the role of aesthetics and agency in Sebald's work.

‘The Claims of Epic: Overcoming historical distance in the Homeric versions of Derek Walcott and Michael Longley’

This book chapter compares the translation strategies of two contemporay poets, Derek Walcott and Michael Longley, as they attempt versions or rewrites of Homeric epic.