Multi-component reactions assemble complex molecules in a highly effective way, however they often suffer from long reaction times. We demonstrate that acceleration of a five-component spiro-pyrrolidine construction can be achieved...
Viscosity modifying agents are one of the most critical components of hydraulic fracturing fluids, ensuring the efficient transport and deposition of proppant into fissures.
13C kinetic isotope effects (KIEs) for the photoredox-promoted
[2 + 2] cycloaddition of enones were determined in homocoupling and
heterocoupling examples. The only significant KIEs were observed at
the β carbon, indicating that Cβ–Cβ bond formation is irreversible. However, these KIEs
were much lower than computational predictions, suggesting that product
selectivity is determined in part by a step prior to Cβ–Cβ bond formation. The results are explained
as arising from a competition between C–C bond formation and
electron exchange between substrate alkenes. This idea is supported
by a relatively small substituent effect on substrate selectivity.
The possible rates for electron transfer and bond-forming steps are
analyzed, and the competition appears plausible, particularly if the
mechanism involves a complex between reduced and neutral enone molecules.
Large intramolecular 13C kinetic isotope effects (KIEs)
for the di-π-methane rearrangement of benzobarrelene fit with
statistical expectations from heavy-atom tunneling when a low-energy
sensitizer is employed, but much lower KIEs are observed with higher-energy
sensitizers. These results in combination with trajectory studies
suggest that the excess vibrational energy available from triplet
energy transfer leads to hot and nonstatistical dynamics in the rearrangement.
The synthesis of water-soluble (η6-arene)ruthenium(II)
complexes based on pyrazolyl–naphthyridine ligands modified
with a carboxylate group is reported. The complexes are easily accessible
in good yields via complexation of [(arene)RuCl2]2 with 7-pyrazolyl-1,8-naphthyridine-2-carboxylic acid (1). All complexes have been characterized by spectroscopic and elemental
analyses. The complexes {[Ru(η6-arene)(
N,N
′-1)Cl]Cl} (arene = benzene
(5), p-cymene (6)) were
further confirmed by X-ray diffraction studies. These complexes are
soluble in water (ca. 10 mg/mL) and are catalytically active in hydrogen-transfer
reduction of carbonyl compounds in aqueous medium with the use of
HCOOH/HCOONa as the hydrogen source.
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