1,374 research outputs found
Rapid Assembly of the Salvileucalin B Norcaradiene Core
Preparation of the polycyclic core of the cytotoxic natural product salvileucalin B is described. The key feature of this synthetic strategy is a copper-catalyzed intramolecular arene cyclopropanation to provide the central norcaradiene. These studies lay the foundation for continued investigations toward an enantioselective total synthesis of 1
Enantioselective Total Synthesis of (+)-Salvileucalin B
An enantioselective total synthesis of the diterpenoid natural product (+)-salvileucalin B is reported. Key findings include a
copper-catalyzed arene cyclopropanation reaction to provide the unusual
norcaradiene core and a reversible retro-Claisen rearrangement of a
highly functionalized norcaradiene intermediate
The scheduling of computer disk operations
There is a growing interest in the application of scheduling techniques to the two mechanical operations which are bottlenecks in the use of movable-head disk storage devices
SeOâ-Mediated Oxidative Transposition of PausonâKhand Products
Oxidative transpositions of bicyclic cyclopentenones mediated by selenium dioxide (SeOâ) are disclosed. Treatment of PausonâKhand reaction (PKR) products with SeOâ in the presence or absence of water furnishes di- and trioxidized cyclopentenones, respectively. Mechanistic investigations reveal multiple competing oxidation pathways that depend on substrate identity and water concentration. Functionalization of the oxidized products via cross-coupling methods demonstrates their synthetic utility. These transformations allow rapid access to oxidatively transposed cyclopentenones from simple PKR products
Cooperative action in eukaryotic gene regulation: physical properties of a viral example
The Epstein-Barr virus (EBV) infects more than 90% of the human population,
and is the cause of several both serious and mild diseases. It is a
tumorivirus, and has been widely studied as a model system for gene
(de)regulation in human. A central feature of the EBV life cycle is its ability
to persist in human B cells in states denoted latency I, II and III. In latency
III the host cell is driven to cell proliferation and hence expansion of the
viral population, but does not enter the lytic pathway, and no new virions are
produced, while the latency I state is almost completely dormant. In this paper
we study a physico-chemical model of the switch between latency I and latency
III in EBV. We show that the unusually large number of binding sites of two
competing transcription factors, one viral and one from the host, serves to
make the switch sharper (higher Hill coefficient), either by cooperative
binding between molecules of the same species when they bind, or by competition
between the two species if there is sufficient steric hindrance.Comment: 7 pages, 6 figures, 1 tabl
Soft systems methodology: a context within a 50-year retrospective of OR/MS
Soft systems methodology (SSM) has been used in the practice of operations research and management science OR/MS) since the early 1970s. In the 1990s, it emerged as a viable academic discipline. Unfortunately, its proponents consider SSM and traditional systems thinking to be mutually exclusive. Despite the differences claimed by SSM proponents between the two, they have been complementary. An extensive sampling of the OR/MS literature over its entire lifetime demonstrates the richness with which the non-SSM literature has been addressing the very same issues as does SSM
A modular approach to prepare enantioenriched cyclobutanes: synthesis of (+)-rumphellaone A
A modular synthesis of enantioenriched polyfunctionalized cyclobutanes was developed that features an 8-aminoquinolinamide directed CâH arylation reaction. The CâH arylation products were derivatized through subsequent decarboxylative coupling processes. This synthetic strategy enabled a 9-step enantioselective total synthesis of the antiproliferative meroterpenoid (+)-rumphellaone A
Asymmetric Michael Addition of Dimethyl Malonate to 2 Cyclopenten-1-one Catalyzed by a Heterobimetallic Complex
A. Preparation of GaNa-(S)-BINOL((S)-2) Solution (0.05 M).2 A flame-dried 1L, three-necked round-bottomed flask with 24/40 joints and a 1.5" Teflon coated egg-shaped magnetic stir bar is brought into a nitrogen filled glovebox (Note 2). The flask is charged with gallium (III) chloride (5.0 g, 28.4 mmol, 1.0 equiv) (Notes 3 and 4). The flask is sealed with three rubber septa (one of which is fitted with an internal temperature probe) brought out of the glovebox, and put under positive pressure of nitrogen via a needle attached to a nitrogen line. Another flame-dried 1L, three-necked round-bottomed flask with 24/40 joints and a 1.5" Teflon coated egg-shaped magnetic stir bar is charged with (S)-(-)-1,1'-bi(2-naphthol) ((S)-BINOL, (S)-1) (16.26 g, 56.8 mmol, 2.0 equiv) (Note 5). The flask is sealed with three rubber septa (one of which is fitted with a thermometer) and evacuated and backfilled with nitrogen three times (5 minutes under vacuum per cycle). A flame-dried 500 mL round-bottomed flask with a 24/40 joint and a 1" Teflon coated egg-shaped magnetic stir bar is charged with sodium tert -butoxide (10.92 g, 113.6 mmol, 4.0 equiv) (Note 6). The flask is sealed with a rubber septum and evacuated and backfilled with nitrogen three times (5 minutes under vacuum per cycle)
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