Capture–Collapse Heterocyclization: 1,3-Diazepanes by C–N Reductive Elimination from Rhodacyclopentanones

Capture–Collapse Heterocyclization: 1,3-Diazepanes by C–N Reductive Elimination from Rhodacyclopentanones

Rhodacyclopentanones derived from carbonylative C-C activation of cyclopropyl ureas can be "captured" by pendant nucleophiles prior to "collapse" to 1,3-diazepanes. The choice of N-substituent on the cyclopropane unit controls the oxidation level of the product, such that C4-C5 unsaturated or saturated systems can be accessed selectively.

Regiospecific reductive elimination from diaryliodonium salts.

StereoElectronic Control of Unidirectional Reductive Elimination (SECURE) is provided by the cyclophane substituent on iodine(III). Computational and experimental studies demonstrate that out of plane steric bulk strongly destabilizes the reductive elimination transition state, and leads to regiochemical control. This approach should be general for high valent main group and transition metal ions.

Photochemical Reductive Elimination of TetrachloroiodateQII)

In analogy to transition metal complexes, coordination compounds of the main group metals can be also classified according to the electron configuration at the metal. Generally, the main group metals occur in oxidation states with so, s2, s2p2 and s2p4 ground states. Recently, we studied the photolysis of so and s2 systems [l-4]. We now report the first results on the photochemistry of an s2p2 ...

Trans influence on the rate of reductive elimination. Reductive elimination of amines from isomeric arylpalladium amides with unsymmetrical coordination spheres.

To determine the trans effect on the rates of reductive eliminations from arylpalladium(II) amido complexes, the reactions of arylpalladium amido complexes bearing symmetrical and unsymmetrical DPPF (DPPF = bis(diphenylphosphino)ferrocene) derivatives were studied. THF solutions of LPd(Ar)(NMeAr') (L = DPPF, DPPF-OMe, DPPF-CF3, DPPF-OMe,Ph, DPPF-Ph,CF3, and DPPF-OMe,CF3; Ar = C6H4-4-CF3; Ar' = ...

Reductive elimination of ether from T-shaped, monomeric arylpalladium alkoxides.