The Diels–Alder reaction of β-fluoro-β-nitrostyrenes with cyclic 1,3-dienes was investigated. A series of novel monofluorinated norbornenes was prepared in up to 97% yield. The reaction with 1,3-cyclohexadiene permits the preparation of monofluorinated bicyclo[2.2.2]oct-2-enes. The kinetic data of the reactions with 1,3-cyclopentadiene and 1,3-cyclohexadiene were used to calculate activation parameters. Furthermore, the synthetic utility of the cycloadducts obtained was demonstrated.
Photoirradiation of a binary cocrystal composed of two different cyclic dienes generates a highly-symmetric cubane-like tetraacid cage regioselectively and in quantitative yield. The cage forms by a double [2+2] photodimerization...
The
Diels-Alder reaction of β-fluoro-β-nitrostyrenes with cyclic 1,3-dienes was
investigated. A series of novel monofluorinated norbornenes was prepared in up
to 97% yield. The reaction with 1,3‑cyclohexadiene permits the preparation of
monofluorinated bicyclo[2.2.2]oct-2-enes. The kinetic data of the reaction with
cyclopentadiene and cyclohexadiene-1,3
were used to calculate activation parameters. Furthermore, the synthetic
utility of the cycloadducts obtained was demonstrated.
The
Diels-Alder reaction of β-fluoro-β-nitrostyrenes with cyclic 1,3-dienes was
investigated. A series of novel monofluorinated norbornenes was prepared in up
to 97% yield. The reaction with 1,3‑cyclohexadiene permits the preparation of
monofluorinated bicyclo[2.2.2]oct-2-enes. The kinetic data of the reaction with
cyclopentadiene and cyclohexadiene-1,3
were used to calculate activation parameters. Furthermore, the synthetic
utility of the cycloadducts obtained was demonstrated.
1-Phenylphosphol-2-ene 1-oxide is effectively resolved by L-menthyl bromoacetate to afford both SP and RP enantiomers of 1-phenylphosphol-2-ene 1-oxide on a multigram scale. The resolved 1-phenylphosphol-2-ene oxide has been found to undergo face-selective and endo-selective cycloadditions with a series of acyclic and cyclic dienes to produce enantiopure P-stereogenic C-P heterocycles of hexahydrophosphindole and hexahydrobenzophosphindole as well as phospha[5.2.1.02,6]decene and phospha[5.2.2.02,6]undecene structures. Conversions of these cycloadducts to the fully saturated heterocyclic systems as well as to their P (III), P = S, P = Se and P-BH3 derivatives have been demonstrated to occur with retention of configuration and preservation of configurational homogeneity at P. A perplexing case of stereomutation at P during reduction of a tricyclic β-hydroxy phosphine oxide by PhSiH3 at 80 °C has been recorded.
Diels–Alder reaction of β-fluoro-β-nitrostyrenes with cyclic dienes
