32 research outputs found
The Normal Red Letter, volume 6, number 1, October (1904)
https://red.mnstate.edu/normalredletter/1032/thumbnail.jp
Transition Spectra for a BCS Superconductor with Multiple Gaps: Model Calculations for MgB_2
We analyze the qualitative features in the transition spectra of a model
superconductor with multiple energy gaps, using a simple extension of the
Mattis-Bardeen expression for probes with case I and case II coherence factors.
At temperature T = 0, the far infrared absorption edge is, as expected,
determined by the smallest gap. However, the large thermal background may mask
this edge at finite temperatures and instead the secondary absorption edges
found at Delta_i+Delta_j may become most prominent. At finite T, if certain
interband matrix elements are large, there may also be absorption peaks at the
gap difference frequencies | Delta_i-Delta_j | . We discuss the effect of
sample quality on the measured spectra and the possible relation of these
predictions to the recent infrared absorption measurement on MgB_2
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A Concise Enantioselective Approach to Quassinoids
A synthetic approach to quassinoids is described. The route to the tetracyclic core relies on an efficient and selective annulation between two unsaturated carbonyl components that is initiated by catalytic hydrogen atom transfer from an iron hydride to an alkene. Application of this strategy allows for enantioselective synthesis of quassin, which is prepared in 14 steps from commercially available starting material
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New Methods and Strategies in the Synthesis of Terpenoid Natural Products
Indoloterpenoids of the paxilline type belong to a large family of secondary metabolites that exhibit unique molecular architectures and a diverse set of biological activities. More than 100 congeners identified to date share a common structural motif that contains an indole moiety fused to a rearranged diterpenoid fragment. The representative physiological and cellular effects attributed to this family of natural products include neurological and insecticidal activities, modulation of lipid balance, and inhibition of mitosis. The uniting polycyclic motif combined with the diversity of individual structural features of paxilline indoloterpenoids and the broad scope of their biological activities have fascinated organic chemists for the past four decades and have led to the development of numerous syntheses. In this Account, we describe our contributions to this field and how they in turn shape new directions that are developing in our laboratory.We begin with the discussion of our strategy for the synthesis of the shared indoloterpenoid core. To address stereochemical challenges encountered in earlier reports, we planned to leverage a suitably substituted cyclopentanone in a polycyclization to form the desired trans-decalin motif. This polycyclization relied on a radical-polar crossover cascade initiated by hydrogen atom transfer. The original process exhibited poor diastereoselectivity, but we discovered an efficient solution to this problem that took advantage of intramolecular tethering effects, culminating in short synthesis of emindole SB. During these studies, we also identified indium-mediated alkenylation of silyl enol ethers with alkynes as a suitable method for the synthesis of highly substituted β,γ-unsaturated ketones that was critical to achieving brevity of our route. We subsequently developed a catalytic version of this transformation that allowed for a formal bimolecular ene reaction that exhibited unusual and potentially useful selectivity in construction of quaternary centers.To test the scope and limitations of our approach to paxilline indoloterpenoids and identify potential improvements, we developed a synthesis of the more complex congener nodulisporic acid C. The convergent assembly of this natural product was enabled by identification of new elements of stereocontrol in the radical-polar crossover polycyclization en route to the polycyclic terpenoid motif and development of a highly diastereoselective enyne cycloisomerization to access the indenopyran motif and a ketone arylation protocol to unite the two complex fragments.In subsequent studies, we expanded the radical-polar crossover cascade underlying our approach to paxilline indoloterpenoids to a bimolecular setting, which allowed for annulation of two unsaturated carbonyl components to produce functionalized cyclohexanes. This transformation is particularly well suited for installation of fully substituted carbons and can be complementary to the venerable Diels-Alder reaction. The utility of the new annulation was tested in the synthesis of forskolin, allowing for rapid construction of the complex polycyclic motif in this densely functionalized labdane diterpenoid.Over the past five years, our initial forays into the synthesis of paxilline indoloterpenoids have grown into a program that incorporates development of new synthetic methods and pursues artificial assembly of terpenoid natural products from several different families. We are encouraged by the increasing diversity of structural motifs made accessible by application of this chemistry and continue to discover new aspects of the underlying reactivity
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Synthesis of Pleuromutilin
Synthesis of a potent inhibitor of bacterial protein synthesis, pleuromutilin, is described. Assembly of the critical cyclooctane fragment relies on an oxidative ring-expansion, and complete stereochemical relay in the synthetic sequence is enabled by the judicious choice of tactics. The requisite connectivity pattern of the perhydroindanone motif is rapidly established in a sequence of cycloaddition and radical cyclization events. Application of this strategy allows for preparation of the target natural product in 16 steps from commercially available material
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Catalytic enantioselective conjugate addition en route to paxilline indoloterpenoids
Development of enantioselective synthesis of precursor en route to paxilline indoloterpenoids is described. Evaluation of 25 diphosphine-based ligands has led to identification of JosiPhos derivative that allows for asymmetric conjugate addition of homoprenyl Grignard reagent to 2-methylcyclopent-2-en-1-one in excellent yield and with appreciable levels of enantioinduction. Application to the conjugate addition of other Grignard reagents is demonstrated
Synthesis of a Potent Antimalarial Amphilectene
7-Isocyano-11Â(20),14-epiamphilectadiene,
the most potent of antimalarial
amphilectenes, is synthesized in seven steps from readily available
materials. The synthesis is enabled by a new dendrimeric triene (Danishefsky
[3]-dendralene) and a new method for stereo- and chemoselective isocyanation.
This chemistry provides a useful entry into an underexplored yet promising
family of antimalarial terpenoids
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Twelve-Step Asymmetric Synthesis of (−)-Nodulisporic Acid C
A short, enantioselective synthesis of (-)-nodulisporic acid C is described. The route features two highly diastereoselective polycyclizations en route to the terpenoid core and the indenopyran fragment and a highly convergent assembly of a challenging indole moiety. Application of this chemistry allows for a 12-step synthesis of the target indoloterpenoid from commercially available material
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A Catalytic Intermolecular Formal Ene Reaction between Ketone-Derived Silyl Enol Ethers and Alkynes
A catalytic formal ene reaction between ketone-derived silyl enol ethers and terminal alkynes is described. This transformation is uniquely capable of bimolecular assembly of 2-siloxy-1,4-dienes and can be used to access β,γ-unsaturated ketones containing quaternary carbons in the α-position