Norbornadiene

About: Norbornadiene is a research topic. Over the lifetime, 2389 publications have been published within this topic receiving 38603 citations.

Valence isomerization of quadricyclane catalyzed by bis(.mu.-acetato)-bis(norbornadiene)dirhodium: evidence for a rhodocyclobutane intermediate

Abstract: Quadricyclane isomerization is catalyzed by red-orange (Rh(NBD)(AcO))/sub 2/ to give norbornadiene (75%) and two endo bis(norbornadienes), 1 (23%) and 2 (2%), at 25/sup 0/C. The reaction is characterized by the formation and disappearance of yellow Rh(III) intermediates. In CH/sub 2/Cl/sub 2/ at 25/sup 0/C the rate law -d(Q)/dt = (0.64 s/sup -1/)(Cat)/sub 0/ adequately describes the results of kinetic studies carried out in the presence of large excesses of Q and NBD and with (Cat)/sub 0/ > 10/sup -4/ M. At -50/sup 0/C rhodocyclohexane intermediates in the formation of dimers were detected and characterized by /sup 1/H and /sup 13/C)/sup 1/H) NMR spectra. The results are consistent with a stepwise mechanism involving insertion of Rh(I) into a cyclopropyl ring to form a rhodocyclobutane intermediate. 4 figures, 3 tables.

Diastereoselective addition of monoterpenic alcoholates and thiolates to 2,3-dicarbomethoxynorbornadiene

Abstract: Addition of excess lithium salts of (−)-menthol or (−)-borneol to 2,3-dicarbomethoxynorbornadiene 1 affords the transesterification–addition products 4 and 5 . The thiols derived from the same monoterpenes give only the addition products to the activated double bond, 6 and 7 . In all cases, the addition reaction is totally exo -selective with respect to the norbornadiene moiety and moderately selective in discriminating the si- and re -face of the double bond. Both diastereomeric products are formed as a mixture of endo–exo epimers at C3. The major addition product of (−)-menthol to 1 is crystalline, of known absolute configuration, and has potential as a precursor of chiral ligands.

Pd/P/dba-Promoted cascade annulations to produce fused medium-sized sulfoximine polyheterocycles

Abstract: The Pd-catalyzed multicomponent reactions of NH-sulfoximine, aryl iodide and norbornadiene (NBD) are reported to chemoselectively produce fused medium-sized sulfoximine polyheterocycles in good to excellent yields. The addition of the dibenzylideneacetone (dba) ligand was found to be useful for this tandem annulation reaction. Under the optimized conditions, a broad range of 3D-type heterocyclic sulfoximines with good functional group tolerance were generated.

Dinickel Active Sites Supported by Redox-Active Ligands.

Abstract: Redox reactions that take place in enzymes and on the surfaces of heterogeneous catalysts often require active sites that contain multiple metals. By contrast, there are very few homogeneous catalysts with multinuclear active sites, and the field of organometallic chemistry continues to be dominated by the study of single metal systems. Multinuclear catalysts have the potential to display unique properties owing to their ability to cooperatively engage substrates. Furthermore, direct metal-to-metal covalent bonding can give rise to new electronic configurations that dramatically impact substrate binding and reactivity. In order to effectively capitalize on these features, it is necessary to consider strategies to avoid the dissociation of fragile metal-metal bonds in the course of a catalytic cycle. This Account describes one approach to accomplishing this goal using binucleating redox-active ligands.In 2006, Chirik showed that pyridine-diimines (PDI) have sufficiently low-lying π* levels that they can be redox-noninnocent in low-valent iron complexes. Extending this concept, we investigated a series of dinickel complexes supported by naphthyridine-diimine (NDI) ligands. These complexes can promote a broad range of two-electron redox processes in which the NDI ligand manages electron equivalents while the metals remain in a Ni(I)-Ni(I) state.Using (NDI)Ni2 catalysts, we have uncovered cases where having two metals in the active site addresses a problem in catalysis that had not been adequately solved using single-metal systems. For example, mononickel complexes are capable of stoichiometrically dimerizing aryl azides to form azoarenes but do not turn over due to strong product inhibition. By contrast, dinickel complexes are effective catalysts for this reaction and avoid this thermodynamic sink by binding to azoarenes in their higher-energy cis form.Dinickel complexes can also activate strong bonds through the cooperative action of both metals. Norbornadiene has a ring-strain energy that is similar to that of cyclopropane but is not prone to undergoing C-C oxidative addition with monometallic complexes. Using an (NDI)Ni2 complex, norbornadiene undergoes rapid ring opening by the oxidative addition of the vinyl and bridgehead carbons. An inspection of the resulting metallacycle reveals that it is stabilized through a network of secondary Ni-π interactions. This reactivity enabled the development of a catalytic carbonylative rearrangement to form fused bicyclic dienones.These vignettes and others described in this Account highlight some of the implications of metal-metal bonding in promoting a challenging step in a catalytic cycle or adjusting the thermodynamic landscape of key intermediates. Given that our studies have focused nearly exclusively on the (NDI)Ni2 system, we anticipate that many more such cases are left to be discovered as other transition-metal combinations and ligand classes are explored.