Strained polycycles by H5C5x free-radical cascades

[reaction: see text] An H(5)C(5x)-type free-radical chain reaction selectively generates up to three new bonds and three new stereocenters in one pot. This previously unexploited strategy provides a straightforward route to the tricyclic cyclopenta[c]indene skeleton, present in a wide range of pharmacologically active natural products, and can significantly simplify the synthesis of other strained polycyclic structures by sidestepping protection, deprotection, and functional group interconversion steps.     

Crystallization of titania ultra-fine particles from peroxotitanic acid in aqueous solution in the present of polymer and incorporation into poly(methyl methacylate) via dispersion in organic solvent

We report a novel strategy for incorporation of titanium dioxide (TiO₂) particles, which were crystallized from peroxotitanic acid in the presence of hydrophilic polymer by hydrothermal treatment in aqueous solution, into poly(methyl methacrylate) (PMMA) via dispersion into chloroform. Dispersion of TiO₂ particles into chloroform was achieved by solvent change from water to chloroform in aid of amphiphilic polymer dispersant, poly(N-vinyl pyrrolidone) (PVP), poly(N-vinyl pyrrolidone-co-methyl methacrylate) (PVP-co-PMMA), poly(N-vinyl pyrrolidone-block-methyl methacrylate) (PVP-b-PMMA) through azeotropical removal of water. Incorporation of TiO₂ particles into PMMA was carried out by a casting process of a mixture of TiO₂ particles dispersed with PVP₁₅₄-b-PMMA₁₅₆ in chloroform and PMMA on a glass substrate. Resultant hybrid film containing TiO₂ less than 10 wt.% showed high transparency in visible region attributable to homogeneous dispersion into PMMA matrix. The refractive index of the hybrid films increased with TiO₂ content and agreed with the calculated values.     

Copper-catalyzed gamma-selective and stereospecific substitution reaction of allylic carbonates with diboron: efficient route to chiral allylboron compounds

A copper-catalyzed gamma-selective and stereospecific substitution reaction of allylic carbonates with a diboron reagent affording allylboron compounds is described. Boryl group was selectively introduced at the gamma-position of the leaving carbonate group. Functionalized allylboronates that have an acetal, ester, or isolated alkene were prepared. The reaction of optically active allylic carbonates underwent complete alpha-to-gamma chirality transfer with anti-stereochemistry to produce optically active allylboronates having a boron-substituted stereogenic center.     

Photoluminescence of strained-layer superlattices

The strained-layer superlattices (SLS's) of In_xGa_1?xAsGaAs and the single hetero-structure of In_xGa_1?xAs on GaAs were grown by MBE method. The samples obtained have a perfect surface morphology. The alloy composition of In_xGa_1?xAs layer and the growth rate were determined with high accuracy by in situ observation of the intensity oscillation of RHEED pattern. Photoluminescence peak energies of SLS's are in agreement with the calculated value by the Kronig-Penny analysis.     

(2,3)-Wittig sigmatropic rearrangements in steroid synthesis. New stereocontrolled approach to steroidal side chains at C-20

A new method which is based on (2-3)-Wittig sigmatropic rearrangements for the stereocontrolled synthesis of functionalized three-carbon side chains on the basic tetracyclic steroidal system is described.     

Synthesis of novel analogues of 1alpha,25-dihydroxyvitamin D(3) with side chains at C-18

Novel analogues of the hormone 1alpha,25-(OH)(2)-D(3) with side chains attached to C-18 were synthesized by a versatile route in which key steps were the remote radical-induced functionalization of the 18-methyl by the C-8beta-hydroxyl group and the introduction of the side chains by Wittig reactions on a C-18-aldehyde. The triene system of the novel analogues was constructed by the convergent Lythgoe-Hoffmann la Roche approach, which involves reaction of a phosphine oxide (the ring A fragment) with a ketone (the upper fragment).     

Pd-catalyzed carbocyclization-Negishi cross-coupling cascade: a novel approach to 1alpha,25-dihydroxyvitamin D3 and analogues

[reaction: see text] A mild palladium-catalyzed cascade has been used for the synthesis of the hormone 1alpha,25-dihydroxyvitamin D3 (calcitriol, 1a) and its analogues 1b and 1c. This one-pot process involves two consecutive transformations at room temperature: An initial palladium-catalyzed 6-exo-cyclocarbopalladation of vinyl triflates followed by a Negishi cross-coupling reaction with an alkenyl zinc. This novel strategy opens new possibilities for the preparation of a variety of new vitamin D analogues of therapeutic potential, particularly with modifications at the triene and/or ring-A.