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281.
Previous attempts to synthesize boracyclanes in the medium-ring range (9-, 10-, 11-, and 12-ring members) via cyclic hydroboration of α,ω-dienes have failed. However, their synthesis via the sequential one-carbon homologation of B-methoxyboracyclanes has been achieved utilizing the successive reaction of B-methoxyboracyclanes with in situ generated (chloromethyl)lithium (LiCH2Cl): MeOB(CH2)5 → MeOB(CH2)6 → MeOB(CH2)7 → MeOB(CH2)8 → MeOB(CH2)9 → MeOB(CH2)10 → MeOB(CH2)11. The yields achieved are in the range of 75–85%. In each case the products are identified by conversion via the DCME reaction into the known cycloalkanones. This development provides the first entry into boracyclanes of the strained medium ring range. 相似文献
282.
Herbert C. Brown P. Veeraraghavan Ramachandran J. Chandrasekharan 《Heteroatom Chemistry》1995,6(2):117-131
A series of diisopinocampheylhaloboranes and monoisopinocampheyldihaloboranes were synthesized by the reaction of the corresponding boranes with the respective HX or X2 (X = halogen) or by the hydroboration of α-pinene with the corresponding haloboranes. Stabilities of these haloboranes in various solvents were studied. Most of these haloboranes proved capable of reducing prochiral ketones to the alcohols with significant optical induction. When tested against a representative aromatic and aliphatic prochiral ketone, acetophenone and 3-methyl-2-butanone, respectively, α-phenethyl alcohol in 65–98% ee and 3-methyl-2-butanol in 28–59% ee were obtained. Some of them exhibited anomalous behavior. 相似文献
283.
Natalie Hell Peter Beiersdorfer Gregory V. Brown Megan E. Eckart Richard L. Kelley Caroline A. Kilbourne Maurice A. Leutenegger Thomas E. Lockard F. Scott Porter Jörn Wilms 《X射线光谱测定》2020,49(1):218-233
X-ray astronomy and ground-based atomic physics have a long history of fruitful collaboration: Sound understanding of the underlying atomic physics is the key to reliable interpretation of the spectra from celestial sources; conversely, astronomical spectra have been used to benchmark and advance atomic physics. This interplay is about to become even more important as we enter a new era of high-resolution X-ray astrophysics with large effective collection area. Although high-resolution observations with the gratings on the Chandra and XMM-Newton observatories continue to drive new science, upcoming planned and proposed missions will open up new discovery space in the near future that is currently challenging to access: high-resolution spectroscopy on extended sources, in the Fe K band, and on short time scales. This review summarizes open questions in these areas and the design parameters for the Hitomi, XRISM, Athena, and Arcus observatories. The expected high quality of spectra taken with these observatories puts new constraints on the accuracy of atomic reference data required to take full advantage of the diagnostic potential of these spectra. 相似文献
284.
Stanelle RD Mignanelli M Brown P Marcus RK 《Analytical and bioanalytical chemistry》2006,384(1):250-258
Microbore columns utilizing polypropylene capillary-channeled polymer (C-CP) fibers as the stationary phase in high-performance
liquid chromatography (HPLC) have been investigated. The polypropylene C-CP fiber diameter is ∼50 μm, with eight channels
along the periphery of the fiber ranging in diameter from ∼12 to 35 μm. The polypropylene C-CP fibers were packed into fluorinated
ethylene propylene (FEP) tubing, 1.3 mm inner diameter, with lengths of 500, 750, and 1,000 mm, to examine the effects of
increased column length with regards to plate height, resolution and analysis time. The low backpressures characteristic of
the C-CP fiber stationary phases allow the length of the column to be increased without significantly decreasing the specific
permeability. The high specific permeability (∼5×10−8 cm2) of the C-CP packed microbore columns yields a relatively low backpressure of 2.35 MPa at the highest flow rate of 17 μL/s
(54 mm/s) for a 1,000 mm column. Radial compression of the soft-walled FEP tubing is accomplished by pulling the 1.7 mm o.d.
column through a 1.4 mm diameter orifice. Reducing the inner diameter of the column from 1.3 to 1.0 mm lowered the interstitial
fraction from 47% to 42%, decreased the A-term contributions to band broadening, resulted in a significant decrease in average
plate height (∼30%), and increased resolution (∼36%) at identical linear velocities. Although the lower void volume of the
radially compressed column increased the backpressure from 0.57 to 2.11 MPa at a linear velocity of ∼20 mm/s, the specific
permeability only decreased from ∼7×10−8 to 4×10−8 cm2.
相似文献
285.
Stephen Brown Ronald Grigg Joanne Hinsley Stewart Korn Visuvanathar Sridharan Michael D. Uttley 《Tetrahedron》2001,57(52):809-10355
A wide variety of aryl/heteroaryl iodides undergo an intermolecular Heck reaction with alkylallenes to furnish 1,3-dienes. These subsequently react in situ with various dienophiles to give Diels–Alder adducts. The chemistry has been extended to incorporate cyclisation-anion capture methodology and the stereochemistry of the products has been determined. 相似文献
286.
287.
T. F. Watson D. Belić P. Y. Convers E. J. Boyd S. A. Brown 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2011,61(1):81-85
Thin films produced by depositing tin clusters with sizes between 5 and 10 nm onto silicon nitride substrates were found to
be
highly coalesced resulting in grains with sizes ~30 nm. Exposing the clusters to nitrogen before they were deposited significantly
reduced the coalescence between them and resulted in granular films where the clusters mostly retained their shape. This is
due to a small
amount of tin nitride forming in the clusters. The coalesced and granular films were used to fabricate tin oxide gas sensors.
This was
done by depositing the two types of films onto silicon nitride chips and then oxidising them by baking at 250 °C for 24 h.
It was found that the sensors composed of uncoalesced clusters were much more sensitive to hydrogen. This was attributed to
the smaller grain size and the larger surface area of the granular films. 相似文献
288.
289.
Dr. Erin N. Hancock Prof. M. Kevin Brown 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(2):565-576
The ladderane family of natural products are well known for their linearly concatenated cyclobutane skeletal structure. Owing to their unique carbocyclic framework, several chemical syntheses have been reported since their discovery in 2002. The focus of this review is to showcase the novel tactics that have been used to generate the ladderane core and the challenges that are associated with the synthesis of these unusual and complex natural products. 相似文献
290.