Pentagon stability: cyclic delocalization of lone pairs through sigma conjugation and design of polycyclophosphanes

The orbital-phase theory was applied to propose pentagon stability in a well-defined manner. Cyclic delocalization of the lone pair electrons on the five-membered ring atoms through the vicinal sigma bonds was shown to be favored by the orbital-phase properties. The pentagon stability was found to be outstanding in saturated phosphorus five-membered rings in the puckered conformation, and was substantiated by the negative strain energy of cyclopentaphosphane, P(5)H(5) (3). The relative increments of the remarkable increase in the strain energies of protonation on the different atoms in the most stable conformers supported the significance of the cyclic delocalization of the lone pairs. Pentagon stability led to the design of three novel polycyclic phosphanes, P(12)H(4) (18), P(13)H(3) (19), and P(14)H(2) (20), with low strain energies due to many puckered pentagon units in them. The low stability of the dodecahedron P(20) (22) was suggested by the high strain energy due to its planar pentagon units. The pentagon stability is less significant in the saturated nitrogen ring molecules due to the greater energy gap between the n and sigma orbitals.     

Radical cascade reaction with 1,4-dienes and 1,4-enynes using 2-(iodomethyl)cyclopropane-1,1-dicarboxylate as a homoallyl radical precursor: one-step synthesis of bicyclo[3.3.0]octane derivatives

[reaction: see text] Radical cascade reaction with various 1,4-dienes and 1,4-enynes using dimethyl 2-(iodomethyl)cyclopropane-1,1-dicarboxylate as a homoallyl radical precursor smoothly proceeds through an iodine atom transfer mechanism to give functionalized bicyclo[3.3.0]octane derivatives in good yields.     

Nef Divisors in Codimension One on the Moduli Space of Stable Curves

Let M _g be the moduli space of smooth curves of genus g 3, and M¯ _g the Deligne-Mumford compactification in terms of stable curves. Let M¯ _g ^[1] be an open set of M¯ _g consisting of stable curves of genus g with one node at most. In this paper, we determine the necessary and sufficient condition to guarantee that a -divisor D on M¯ _g is nef over M¯ _g ^[1], that is, (D · C) 0 for all irreducible curves C on M¯ _g with C M¯ _g ^[1] .     

Hyperfine structure of the electron spin resonance of phosphorus-doped Si nanocrystals

Electronic states of P donors in Si nanocrystals (nc-Si) embedded in insulating glass matrices have been studied by electron spin resonance. Doping of P donors into nc-Si was demonstrated by the observation of optical absorption in the infrared region due to intraconduction band transitions. P hyperfine structure (hfs) was successfully observed at low temperatures. The observed splitting of the hfs was found to be much larger than that of the bulk Si:P and depended strongly on the size of nc-Si. The observed strong size dependence indicates that the enhancement of the hyperfine splitting is caused by the quantum confinement of P donors in nc-Si.     

Synthesis of phosphorus‐containing vinyl ether monomers and oligomers and their photoinitiated polymerization

Divinyl ether monomers containing phosphorous residues were synthesized by the addition reaction of glycidyl vinyl ether (GVE) with various phosphonic dichlorides or dichlorophosphates with quaternary onium salts as catalysts. The reaction of GVE with phenylphosphonic dichloride gave bis[1‐(chloromethyl)‐2‐(vinyloxy)ethyl]phenylphosphonate ( 1a ) in a 77% yield. The polycondensation of 1a with terephthalic acid was also carried out with 1,8‐diazabicyclo[5.4.0]undecene‐7 (DBU) as a condensing agent to afford the corresponding phosphorus‐containing polyester. A multifunctional monomer containing both vinyl ether groups and methacrylate groups was prepared by the reaction of 1a with methacrylic acid with DBU. The photoinitiated cationic polymerization of these vinyl ether compounds proceeded rapidly with bis[4‐(diphenylsulfonio)phenyl]sulfide‐bishexafluorophosphate as the cationic photoinitiator without a solvent upon ultraviolet irradiation. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2031–2042, 2004     

Molecular-level chiral discrimination and induction

The review describes the mechanism of chiral discrimination of racemic amines upon crystallization and the induction of chirality in organic reactions by using them as chiral auxiliaries. In order to form conglomerates, which can be resolved into the two enantiomers upon alternative seeding, both formation and packing of 2₁-columns are essentially very important. On the other hand, in order to achieve high efficiency in resolution through diastereomeric salt formation, which is the most practical method, one of a pair of diastereomeric salts derived from a racemic amine and an enantiomerically pure resolving agent should at least have two 2₁-columns and planar boundary surfaces in its crystal structure. On the basis of this knowledge, we developed several artificial chiral auxiliaries such as erythro-2-amino-1,2-diphenylethanol,cis-2-amino-1-acenaphthenol, andcis-2-amino-3,3-dimethyl-1-indanol. These were found to be very efficient chiral auxiliaries in asymmetric inductions: alkylation of chiral imines, catalytic borane-reduction, and alkylation of chiral N-acylated oxazolidinone.