Linear N-alkenyl or alkynyl N-sulfonyl 1-aminobut-3-yn-2-ones are converted into bicyclic indolizines and pyrrolo1,2-aazepine-type alkaloids upon gold(I) catalysis (17 examples, 10–85%). The ...reaction cascade allowed formation of C–N, O–S, and C–C bonds via a cycloisomerization/sulfonyl migration/cyclization process using 10 mol % of (2-biphenyl)di-tert-butylphosphinegold(I) triflimide complex in dichloromethane.
In this paper we are reporting the first regio- and stereoselective silylformylation of ynamides. This reaction is tolerant to a wide range of functional groups around the ynamides. The substitution ...of CO by an isocyanide makes this reaction safer and more practical than standard silylformylation reactions. It overall represents a versatile and rapid access to various tetrasubstituted 3-silyl-2-amidoacrolein derivatives. The synthetic potential of these new building blocks has been evaluated by performing several postfunctionalization.
In this paper we report the annulation reaction between 2-iodobenzaldehyde derivatives and various ynamides. This palladium-catalyzed reaction leads to rare polysubstituted amino-indenones in good ...yields with a regioselectivity up to complete. Remarkably, a regiodivergent selectivity has been identified between aryl and alkyl or silyl ynamides, with the first leading mainly to 2-amido-indenones and the second to 3-amido-indenones.
In this manuscript we report the synthesis of 3‐amido‐benzobsilines thanks to a 2‐step strategy involving a 3‐component silylformylation of ynamides followed by a Friedel‐Crafts ...cyclization/isomerizing dehydration domino sequence. This reaction is tolerant to various structural variations and has allowed us to synthesize a library of diversely substituted silacycles with yields from 33 to 85%. We also studied the fluorescence properties of these compounds which show structural similarities with recognized probes such as Si‐Rhodamine for example.
Nickel(0) nanoparticles coordinated to NHC ligands bearing N-coordinated cinnamyl moieties were readily prepared by reduction of a NiCpBr(NHC-cinnamyl) complex with methyl magnesium bromide. The ...combination of a strong σ-donor NHC ligand with a π-coordinating appended cinnamyl moiety likely prevents nickel(0) nanoparticle aggregation to larger inactive species, and allows the effective and (
Z
)-selective semi-hydrogenation of alkynes and ynamides
.
Nickel(0)-NHC nanoparticles bearing cinnamyl moieties catalyse effectively (
Z
)-selective semi-hydrogenations.
In this manuscript we report the synthesis of 3‐amido‐benzobsilines thanks to a 2‐step strategy involving a 3‐component silylformylation of ynamides followed by a Friedel‐Crafts ...cyclization/isomerizing dehydration domino sequence. This reaction is tolerant to various structural variations and has allowed us to synthesize a library of diversely substituted silacycles with yields from 33 to 85%. We also studied the fluorescence properties of these compounds which show structural similarities with recognized probes such as Si‐Rhodamine for example.
Alveolar echinococcosis (AE) of the liver is a rare and severe parasitic disease. It behaves like a slow-growing liver cancer, and liver transplantation (LT) has been proposed in advanced cases since ...1985. The aim of this retrospective study was to collect all AE transplant cases in Europe, analyze the results, and specify the usefulness of LT for this unusual indication.
A questionnaire was sent to 83 LT centers from July 1996 to December 1999.
Sixty-five centers responded: 45 AE patients (mean age, 45.8 years) underwent an LT procedure at 16 LT centers. The mean interval between diagnosis and LT was 5 years. One patient died during the hepatectomy phase. Five-year survival was 71%. Five-year survival without recurrence was 58%. The nine early deaths were mostly related to bacterial or fungal infections, or both, in patients in bad condition when LT was performed. Six patients had a graft AE reinfection. Five late deaths were related directly to ongoing AE. In the other cases, benzimidazole (BZM) therapy seemed to stabilize AE residues.
This unique experience indicates that LT is feasible for life-threatening AE. Specific management is needed to optimize the results: earlier decision for LT in incurable symptomatic biliary AE, pre- and post-LT BZM therapy, meticulous pre-LT evaluation to identify extrahepatic extension, and an immunosuppressive regimen kept to a minimum.
Alveolar echinococcosis (AE) of the liver, caused by the larval stage of the fox tapeworm Echinococcus multilocularis, has the characteristics of a slow-growing liver cancer. It is one of the rare ...parasitic diseases for which a parasitolytic drug is not yet available, and AE is lethal in the absence of appropriate therapeutic management. Complete surgical resection of the parasite at an early stage of infection provides favourable prospects for cure, but, due to a long clinical latency, many cases are diagnosed at an advanced stage, so that partial liver resection can be performed in only 35% of patients. Benzimidazole (BZM) treatment is given in inoperable cases but these compounds are only parasitostatic, and lifelong therapy is required. During the past 20 years some centres have considered liver transplantation (LT) for the treatment of incurable AE.
Our review summarizes the results of this experience based on a series of 47 European patients who received transplants between 1985 and 2002, tries to specify the real place of LT for AE, and underlines the measures that could be undertaken in the future to improve the results.
Five-year survival was 71%. Five-year survival without recurrence was 58%. Major technical difficulties related either to previous laparotomies or to the loco-regional involvement were observed. The nine early deaths concerned AE patients with a long past-history of symptomatic AE (iterative cholangitis, secondary biliary cirrhosis). Five late deaths were directly related to ongoing AE, located in the brain in three cases, a very rare AE location that was not investigated before LT in these patients.
In general, the pre-LT screening for distant AE metastases appeared insufficient in this series. Heavy immunosuppressive schemes, absence or delayed re-introduction of BZM after LT have clearly played a role in this unfavourable course. This unique experience indicates that, despite major technical difficulties, LT for incurable AE is feasible and could be discussed in very symptomatic cases. Before LT, interventional radiology should be preferred to repeated laparotomies. Pre-LT and post-LT BZM treatment is mandatory. A careful evaluation of possible distant metastases should be done before the decision for LT is made. After LT, the possibility of an ongoing AE must be permanently kept in mind. This could be reduced by lightening the immunosuppressants, carefully following the specific circulating antibodies, and applying a systematic radiological evaluation, not only to the graft but also to the lungs and the brain.
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