A nitrogen-containing superbase such as TMG was found to be an effective catalyst for the reaction between N-diphenylphosphinoyl imines and nitroalkanes. Exploiting a protocol that avoids the use of any solvent also during workup procedure, we synthesized a series of beta-nitroamines in excellent yields and high diastereomeric ratios. These results, combined with the capability of the indium in conjunction with Zn as the stoichiometric reducing agent to perform in aqueous medium reduction of the nitro group under mild reaction conditions, led us to devise a three-step, one-pot synthesis of a range of 1,2-diamines, making use of environmentally friendly procedures in the various steps.

Advanced therapy medicinal products (ATMPs) are potential game changers in modern medical care with an anticipated major impact for patients and society. They are a new drug class often referred to as “living drugs,” and are based on complex components such as vectors, cells and even tissues. The production of such ATMPs involves innovative biotechnological methods. In this survey, we have assessed the perception of European citizens regarding ATMPs and health care in Europe, in relation to other important topics, such as safety and security, data protection, climate friendly energy supply, migration, and others. A crucial question was to determine to what extent European citizens wish to support public funding of innovations in healthcare and reimbursement strategies for ATMPs. To answer this, we conducted an online survey in 13 European countries (representative of 85.3% of the entire EU population including the UK in 2020), surveying a total of 7,062 European citizens. The survey was representative with respect to adult age groups and gender in each country. Healthcare had the highest ranking among important societal topics. We found that 83% of the surveyed EU citizens were in support of more public funding of technologies in the field of ATMPs. Interestingly, 74% of respondents are in support of cross-border healthcare for patients with rare diseases to receive ATMP treatments and 61% support the reimbursement of very expensive ATMPs within the European health care system despite the current lack of long-term efficacy data. In conclusion, healthcare is a top ranking issue for European Citizens, who additionally support funding of new technologies to enable the wider application of ATMPs in Europe.

A N e w a n d P r a c t i c a l P r o c e d u r e f o r t h e B r u y l a n t s R e a c t i o n Abstract: N,N-Disubstituted a-aminonitriles undergo Bruylants reaction under Barbier and Reformatsky conditions with activated halides, in the presence of zinc and 10 mol% HOAc. The high yields and the simple operational conditions make this reaction an appealing approach to N,N-disubstituted homoallylamines and b-aminoesters.a-Aminonitriles are very popular bifunctional compounds useful not only as synthetic intermediates for a-aminoacids, but also as versatile synthons in organic chemistry. 1 The Strecker reaction which involves treatment of aldehydes with ammonia and hydrogen cyanide (or equivalents) provides one of the most popular and widely used routes to a-aminonitriles and has been applied on an industrial scale towards the synthesis of racemic a-aminoacids via hydrolysis of the intermediate a-aminonitriles. Moreover an emerging field of importance deals 2 with direct and viable methods for the synthesis of homochiral aaminonitriles via catalytic asymmetric Strecker-type reactions. Besides these well established methodologies, very recently a Strecker-type aminative cyanation of aldehydes and ketones using bis(dialkylamino)cyanoboranes has been reported 3 disclosing a general and highly flexible new entry to these synthetically useful building blocks (Scheme 1). Regarding the further synthetic elaborations, whereas the hydrolysis and the reduction of the cyano group in N,N-disubstituted a-aminonitriles are well documented, 1a the reaction sequence involving the addition of an organometallic reagent to the nitrile group, with formation of the intermediate imine, is more problematic. As a matter of fact only in particular circumstances 4 the addition reaction prevails over the replacement of the cyano group by a C-nucleophile. The latter pathway, known as Bruylants reaction, is an old widely used procedure 5 for the preparation of a-substituted tertiary amine moieties. 6 In the course of our ongoing research program aimed at the synthesis of new core units for HIV protease inhibitors, 7 we became interested in the synthesis of a-aminonitriles and in their reactivity towards organometallic reagents. Herein we report a general, concise and very simple procedure based on an unprecedented combination between the Bruylants and the Barbier or Reformatskytype reactions, aimed at the straightforward transformation of a-aminonitriles into N,N-disubstituted homoallylic amines and b-aminoesters.The a-aminonitriles 1a-i were synthesized in very good yields following Suginome's procedure 3 (Scheme 1) using simple aldehydes and different bis(dialkylamino)cyanoboranes 8 as starting materials (Table 1). Scheme 1Besides dialkyl substituted aminonitriles, we successfully extended this synthesis to derivatives bearing a reactive framework at nitrogen, e.g. a double bond, and removable groups, such as the benzyl and the p-methoxybenzyl (PMB) groups (entries 7-9).Though several variants in the use of the Bruylants reaction have bee...

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A series of 4-ferrocenyl-and 4-[(S Fc )-2-(p-tolylsulfanyl)ferrocenyl]-β-lactams has been synthesized in good yields by a one-pot reaction of achiral and planar-chiral ferrocenylimines with substituted acetic acids. The acid-induced stereoconvergent transformation of cis-and trans-4-ferrocenyl-