16 research outputs found

    Diastereoselective reduction of α-keto esters derived from functionalised cholic acid

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    The reduction of phenylglyoxalate 2a and pyruvate 2b with LiBH4 in THF at -80 degrees C yield the corresponding alpha-hydroxy esters with ca. 70% diastereoselectivity

    Asymmetric Diels-Alder Reactions of Chiral Acrylates of Cholic Acid Derivatives

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    New steroid-based chiral auxiliaries 6, 9, and 12 have been synthesized from readily available cholic acid. These new chiral auxiliaries place the reactive and the shielding sites in a 1,5 relationship to each other. Diels-Alder reaction of cyclopentadiene with corresponding acrylate esters (7, 10, and 13) have been examined. Acrylates 7 and 10 yielded cycloadducts with 29-88% diastereomeric excess with excellent endo selectivity in the presence of an excess of Lewis acids such as AlCl3, BF3.OEt(2), FeCl3, SnCl4, TiCl4, and ZnCl2. Treatment of acrylate 7 with cyclopentadiene in the presence of BF3.OEt(2) at -80 degrees C gave the endo adduct (>99%) with 88% de. Lewis acid catalyzed and uncatalyzed reactions of acrylates 7 and 10 with cyclopentadiene yielded cycloadducts with opposite stereochemistry. The chiral auxiliary was recovered in a nondestructive manner only via iodolactonization. Acrylate ester of alcohol 12 did not show any selectivity in either catalyzed and uncatalyzed reactions with cyclopentadiene. The presence of a flat aromatic surface at C-7 of the steroid was found to be essential to effect high diastereoselection

    Bile-Acids in Asymmetric-Synthesis.2. Cholic-Acid Derived Novel Chiral Auxiliaries For Asymmetric Diels-Alder Reactions

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    Cholic acid-based chiral acrylate 5 yields a Diels-Alder adduct with cyclopen

    Jet Thrust Vectoring Using a Miniature Fluidic Oscillator

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    This paper presents a new approach to vectoring jet thrust using a miniature fluidic actuator that provided spatially distributed mass addition. The fluidic actuators used had no moving parts and produced oscillatory flow with a square wave form at frequencies up to 1(.)6kHz. A subsonic jet with an exit diameter of 3(.)81cm was controlled using single and dual fluidic actuators, each with an equivalent circular diameter of 1(.)06mm. The fluidic nozzle was operated at pressures between 20(.)68 and 165(.)47kPa. The objectives of the present work included documentation of the actuation characteristics of fluidic devices, assessment of the effectiveness of fluidic devices for jet thrust vectoring, and evaluation of mass flow requirements for vectoring under various conditions. Measurements were made in the flow field using a pitot probe for the vectored and unvectored cases. Some acoustic measurements were made using microphones in the near-field and for selected cases particle image velocimetry (PIV) measurements were made. Thrust vectoring was obtained in low speed jets by momentum effects with fluidic device mass flow rates of only 2 x 10(-4) kg/sec (0-6% of main jet mass flow per fluidic oscillator). Although a single fluidic device produced vectoring of the primary jet, the dual fluidic device configuration (with two fluidic devices on either side of the jet exit) produced mass flux enhancement of 28% with no vectoring. Our results indicate that fluidic actuators have the potential for use in thrust vectoring, flow mixing and industrial flow deflection applications
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