Azadi-π-methane Rearrangement Involving an Oxime Group

Competition between concerted and stepwise dynamics in the triplet di-π-methane rearrangement.

The molecular dynamics of the triplet-state Zimmerman di-π-methane rearrangement of dibenzobarrelene were computed with B3LYP and M06-2X density functionals. All productive quasiclassical trajectories involve sequential formation and cleavage of C-C bonds and an intermediate with lifetimes ranging from 13 to 1160 fs. Both dynamically concerted and stepwise trajectories are found. The average li...

Photoalignment layers for liquid crystals from the di-π-methane rearrangement.

Photoalignment of nematic liquid crystals is demonstrated using a di-π-methane rearrangement of a designed polymer. The alignment mechanism makes use of the strong coupling of the liquid crystal directors to dibenzobarrelene groups. The large structural changes that accompany photoisomerization effectively passivate segments of the polymer, allowing the remaining dibenzobarrelene groups to domi...

Tandem β-elimination/hetero-michael addition rearrangement of an N-alkylated pyridinium oxime to an O-alkylated pyridine oxime ether: an experimental and computational study.

A novel OH(-)-promoted tandem reaction involving C(β)-N(+)(pyridinium) cleavage and ether C(β)-O(oxime) bond formation in aqueous media has been presented. The study fully elucidates the fascinating reaction behavior of N-benzoylethylpyridinium-4-oxime chloride in aqueous media under mild reaction conditions. The reaction journey begins with the exclusive β-elimination and formation of pyridine...

On an Equality Involving Group Characters

a rare de novo complex chromosomal rearrangement (ccr) involving four chromosomes in an oligo-asthenosperm infertile man

complex chromosomal rearrangements (ccrs) are rare events involving more than two chromosomes and over two breakpoints. they are usually associated with infertility or sub fertility in male carriers. here we report a novel case of a ccr in a 30-year-old oligoasthenosperm man with a history of varicocelectomy, normal testes size and normal endocrinology profile referred for chromosome analysis t...