Controlling chemoselectivity in vinyl and allylic C-X bond activation with palladium catalysis: a pK(a)-based electronic switch

It has been demonstrated that the same Pd catalyst can be used to effect allylic substitution or vinylic cross-coupling reactions selectively and interchangeably on polyfunctionalized olefin building blocks despite the differences in reaction mechanism. This was achieved by altering the pK(a) of the conjugate acid of the allylic leaving group while keeping the vinyl coupling partner constant. In the case of 2,3-dibromo-1-propene, Pd-catalyzed allylic ionization with malonate nucleophile proceeded selectively and quantitatively in the presence of the Suzuki reaction components necessary for cross-coupling. Conversely, the bromide of 2-bromo-1-(4-ethylphenoxy)-2-propene could be cross-coupled selectively without activation of the allylic phenoxy substituent. In both reactions, the same catalyst could then be used to complete the sequence, which typically involved heating as the trigger to promote the second, more reluctant reaction. Mechanistic considerations as well as synthetic applications demonstrating the value of this interchangeable catalyzed sequence are presented.     

The enantioselective synthesis of alpha-amino acid derivatives via organoboranes

Optically active (S)-alpha-amino acids are prepared in 54-95% ee (12 cases) by reaction of the Schiff base acetate of glycine tert-butyl ester with B-alkyl-9-BBN derivatives in the presence of the Cinchona alkaloid, cinchonidine, and base. The enantiomeric (R)-alpha-amino acids are available in 59-92% ee (3 cases) by using cinchonine as the chiral control element.     

Vacuum decay constraints on a cosmological scalar field

If the potential of a scalar field phi which currently provides the "dark energy" of the Universe has a minimum at phi = -M(0)(4)<0, then quantum-mechanical fluctuations could nucleate a bubble of phi at a negative value of the potential. This bubble would then expand at the speed of light. Given that no such bubble enveloped us in the past, we find that any minimum in V(phi) must be separated from the current phi value by more than min[1.5M(0),0.21M(Pl)], where M(Pl) is the Planck mass. We also show that vacuum decay renders a cyclic or ekpyrotic universe with M(0)(4) > or approximately 10(-10)M(4)(Pl) untenable.     

Measurement of orientation distributions using chemical shift amplification

A new three-dimensional magic angle spinning (MAS) experiment is proposed, based on a combination of the two-dimensional rotor-synchronized MAS experiment of Spiess and co-workers and a new chemical shift anisotropy amplification method. The new experiment is demonstrated on a macroscopically ordered sample of ultra-high molecular weight poly(ethylene).     

Double-quantum dipolar recoupling at high magic-angle spinning rates

A full investigation of the possible homonuclear double-quantum recoupling sequences, based on the RN family of sequences with N < or = 20, is given. Several new RN sequences, R16(6)(5), R18(8)(5), and R18(10)(5), were applied at high magic-angle spinning rates and compared with theory. The R18(10)(5) technique can be used to recouple dipolar couplings at spinning rates up to 39 kHz, and the application of the sequence in an INADEQUATE experiment is shown for a spinning rate of 30 kHz.     

A Geometric Invariant for Metabelian Pro-p Groups

In [2] Bieri and Strebel introduced a geometric invariant forfinitely generated abstract metabelian groups that determineswhich groups are finitely presented. For a valuable survey oftheir results, see [6]; we recall the definition briefly inSection 4. We shall introduce a similar invariant for pro-pgroups. Let F be the algebraic closure of F_p and U be the formal powerseries algebra F[T], with group of units U^x. Let Q be a finitelygenerated abelian pro-p group. We write Z_p[Q] for the completedgroup algebra of Q over Z_p. Let T(Q) be the abelian group Hom(Q,U^x) of continuous homomorphisms from Q to U^x. We write 1 forthe trivial homomorphism. Each vT(Q) extends to a unique continuousalgebra homomorphism from Z_p[Q]to U.     

Viscoelastic shear properties of in vivo breast lesions measured by MR elastography

Elastography is a technique to assess the viscoelastic properties of tissue by measuring an acoustic wave propagating though the object. Here, the technique is applied in the course of standard MR mammography to 15 patients with different pathologies (six breast cancer cases, six fibroadenoma cases and three mastopathy cases). Low-frequency mechanical waves are coupled longitudinally into the tissue in order to obtain sufficient wave amplitude throughout the entire breast. This leads to the presence of a substantial fraction of compressional waves, which contribute to the total displacement field. It is shown theoretically that the correct evaluation of these contributions from the compressional wave is rather difficult due to the almost incompressible nature of tissue. To overcome this problem, it is proposed to apply the curl-operator to the measured displacement field in order to completely remove contributions from the compressional wave. Results from simulations and a breast phantom demonstrate the feasibility of the technique. The in vivo results show a good separation between breast cancer and benign fibroadenoma utilizing the shear modulus. Breast cancer appears on average 2.2 (P<.001) times stiffer. All breast cancer cases showed a good delineation to the surrounding breast tissue with an average elevation of a factor of 3.3 (P< 1.4 x 10(-6)). The results as obtained for the shear viscosity do not indicate to be useful for separating benign from malignant lesions.