68 research outputs found
Iridium complexes bearing a PNP ligand, favoring facile C(sp^3)āH bond cleavage
Hydrogen iodide is lost upon reaction of PNP with IrI_3, where PNP = 2,6-bis-(di-t-butylphosphinomethyl)pyridine to give crystallographically characterized Ir(PNP)*(I)_2, which reacts with H_2 to give Ir(PNP)(H)(I)_2. Ir(PNP)(Cl)_3 is relatively inert towards the intramolecular CāH activation of the tert-butyl's of the PNP ligand
Acceleration of Nucleophilic CH Activation by Strongly Basic Solvents
(IPI)Ru(II)(OH)_n(H_2O)_m, 2, where IPI is the NNN-pincer
ligand, 2,6-diimidizoylpyridine, is shown to catalyze H/D exchange
between hydrocarbons and strongly basic solvents at higher rates
than in the case of the solvent alone. Significantly, catalysis by 2
is accelerated rather than inhibited by increasing solvent basicity.
The evidence is consistent with the reaction proceeding by base
modulated nucleophilic CH activation
Crystal structure of Li_2B_(12)H_(12): a possible intermediate species in the decomposition of LiBH_4
The crystal structure of solvent-free Li_2B_(12)H_(12) has been determined by powder X-ray diffraction and confirmed by a combination of neutron vibrational spectroscopy and first-principles calculations. This compound is a possible intermediate in the dehydrogenation of LiBH_4, and its structural characterization is crucial for understanding the decomposition and regeneration of LiBH_4. Our results reveal that the structure of Li_2B_(12)H_(12) differs from other known alkali-metal (K, Rb, and Cs) derivatives
Total Synthesis and Structural Verification of Isatindigotindoline C
Total synthesis of the polycyclic alkaloid isatindigotindoline C is achieved in two steps using an exo-selective [3+2]-dipolar cycloaddition. The synthesis verifies the originally computationally assigned relative stereochemistry
Arylboronic Acid-Catalyzed C-Allylation of Unprotected Oximes
Unprotected keto- and aldoximes are readily C-allylated with allyl diisopropyl boronate in the presence of arylboronic acid catalysts to yield highly-substituted N-alpha-secondary (2Ā°) and tertiary (3Ā°) hydroxylamines. The methodās synthetic utility is demonstrated with the total synthesis of the trace alkaloid N-methyl-euphococcine. Preliminary experimental and computational mechanistic studies point toward the formation of a boroxine as the active allylating species.<br /
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