17,507 research outputs found
Stereoselective Synthesis of Densely Substituted Tetrahydroquinolines by a Conjugate Addition Nitro-Mannich Reaction with Carbon Nucleophiles
Conjugate addition of an alkyl group to a series of 2-imino-nitrostyrenes and then addition of trifluoroacetic acid initiates a nitro-Mannich cyclisation to give cis,cis-2,3,4-substituted tetrahydroquinolines in good yield and high diastereoselectivity
A Divergent Synthetic Route to the Vallesamidine and Schizozygine Alkaloids: Total Synthesis of (+)âVallesamidine and (+)â14,15âDehydrostrempeliopine
The total synthesis of representative members of the schizozygine alkaloids, (+)âvallesamidine and (+)â14,15âdehydrostrempeliopine, were completed from a lateâstage divergent intermediate. The synthesis took advantage of efficient nitroâgroup reactions with the A/B/C ring skeleton constructed concisely on a gram scale through an asymmetric Michael addition, nitroâMannich/lactamisation, TsujiâTrost allylation, and intramolecular CâN coupling reaction. Other key features of the synthesis are a novel [1,4] hydride transfer/Mannichâtype cyclisation to build ringâ
E and a diastereoselective ringâclosing metathesis reaction to construct ringâ
D. This approach gave access to a lateâstage C14,C15 alkene divergent intermediate that could be simply transformed into (+)âvallesamidine, (+)â14,15âdehydrostrempeliopine, and potentially other schizozygine alkaloids and unnatural derivatives
Applications of bioluminescence in biotechnology and beyond.
Bioluminescence is the fascinating natural phenomenon by which living creatures produce light. Bioluminescence occurs when the oxidation of a small-molecule luciferin is catalysed by an enzyme luciferase to form an excited-state species that emits light. There are over 30 known bioluminescent systems but the luciferin-luciferase pairs of only 11 systems have been characterised to-date, whilst other novel systems are currently under investigation. The different luciferin-luciferase pairs have different light emission wavelengths and hence are suitable for various applications. The last decade or so has seen great advances in protein engineering, synthetic chemistry, and physics which have allowed luciferins and luciferases to reach previously uncharted applications. The bioluminescence reaction is now routinely used for gene assays, the detection of protein-protein interactions, high-throughput screening (HTS) in drug discovery, hygiene control, analysis of pollution in ecosystems and in vivo imaging in small mammals. Moving away from sensing and imaging, the more recent highlights of the applications of bioluminescence in biomedicine include the bioluminescence-induced photo-uncaging of small-molecules, bioluminescence based photodynamic therapy (PDT) and the use of bioluminescence to control neurons. There has also been an increase in blue-sky research such as the engineering of various light emitting plants. This has led to lots of exciting multidisciplinary science across various disciplines. This review focuses on the past, present, and future applications of bioluminescence. We aim to make this review accessible to all chemists to understand how these applications were developed and what they rely upon, in simple understandable terms for a graduate chemist
Asymmetric Intramolecular Conjugate Addition Nitro-Mannich Route to cis-2-Aryl-3-nitrotetrahydroquinolines
Reductive cyclization of 2-iminonitrostyrenes (from the condensation of 2-aminostyrenes with an aldehyde and subsequent nitration of the alkene) using a bifunctional thiourea catalyst and tert-butyl-Hantzsch ester leads to an intramolecular conjugate hydride addition nitro-Mannich reaction to give the corresponding cis-2-aryl-3-nitrotetrahydroquinolines as single diastereoisomers in high yields and enantioselectivities
Synthesis of planar chiral ferrocenyl cyclopentadienyl chelate ligand precursors
Two families of planar chiral ferrocenyl cyclopentadienyl chelate ligands for use in ansa-half sandwich metallocene complexes of catalytically active transition metals are described. The first family was derived in 4â5 steps from an enzymatic resolution of 1-iodo-2-(methylalcohol)ferrocene and possesses a cyclopentadiene derivative [Cp(H) = 1-indenyl, 2-indenyl or Ph4Cp(H)] directly attached to the ferrocene ring with an adjacent vicinal tether CH2Z donor group (Z = OH, OMe, NHMe, NMe2 or PPh2). The second family was derived from a chiral auxiliary approach and has the donor group (Z = PPh2 or NMe2) attached directly to the ferrocene ring with an adjacent tether vicinal CH2Cp(H) group [Cp(H) = Cp(H), fluorenyl, 1-indenyl, Me4Cp(H) or Ph4Cp(H)]
Propagation of fluctuations in biochemical systems, I: Linear SSC networks
We investigate the propagation of random fluctuations through biochemical networks in which the number of molecules of each species is large enough so that the concentrations are well modeled by differential equations. We study the effect of network topology on the emergent properties of the reaction system by characterizing the behavior of variance as fluctuations propagate down chains and studying the effect of side chains and feedback loops. We also investigate the asymptotic behavior of the system as one reaction becomes fast relative to the others. © 2007 Springer Science+Business Media, Inc
Epidemiological surveys of, and research on, soil-transmitted helminths in Southeast Asia: a systematic review
PRISMA checklist, full list of search terms and Supporting Figure 1. (DOCX 1462ĂÂ kb
Radical cyclisation studies of ÎČ-nitroamines from the nitro-Mannich reaction
A range of novel ÎČ-nitroacetamides with an alkenyl- or alkynyl tether were synthesized using the deprotonative or conjugate addition nitro-Mannich reaction. They were subjected to radical denitration-cyclisation with a 10 equivalent excess of tributyltin hydride, catalytic AIBN in refluxing benzene to explore the structural and electronic requirements for efficient cyclisation. Cyclisations of the ÎČ-nitroacetamides were successful in most cases, undergoing 5-exo-trig cyclisation to give the desired cyclopentyl or indanyl structures. Radical 1,4-translocation of a phenyl group was observed in several cases. Diastereoselectivity was low, with 2 or 3 of 4 possible diastereoisomers observed in most cases. Further purification by crystallisation allowed the isolation of some as single diastereoisomers. It was found that higher yields were obtained by increasing the substitution or reducing the degrees of freedom of the tether between the nitro group and the radical acceptor
Synthesis and bioluminescence of electronically modified and rotationally restricted colour-shifting infraluciferin analogues
Synthetic nIR emitting luciferins can enable clearer bioluminescent imaging in blood and tissue. A limiting factor for all synthetic luciferins is their reduced light output with respect to D-luciferin. In this work we explore a design feature of whether rigidification of an exceptionally red synthetic luciferin, infraluciferin, can increase light output through a reduction in the degrees of freedom of the molecule. A rigid analogue pyridobenzimidazole infraluciferin was prepared and its bioluminescence properties compared with its non-rigid counterpart benzimidazole infraluciferin, luciferin, infraluciferin and benzimidazole luciferin. The results support the concept that synthetic rigidification of Ï-extended luciferins can increase bioluminescence activity while maintaining nIR bioluminescence
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