Heaton et al., "Palladium(II)/[beta]-diketonate complexes containing the enolates
of N-acetyl-3-acyltetramic acids: crystal structure of the Lewis base adduct, [Pd(py)4](abta)2," Inorganica Chimica Acta, vol.
from 1-indanone (generated in homogeneous phase, using LDA as the base) reacted with the methylsulfinyl chloride to form the keto sulfoxide in one step .
However, the supposedly more accurate calculations with 6-311++g(3d,3p) basis set did not reproduce lowering of enolization energy with an explicit water molecule placed close to the oxygen atom of the enolate and ketone (Table 4).
Negative results obtained under the same aqueous conditions with other reactive electrophiles (see supporting information), including electrophiles known to give products in reaction with tropinone enolates (e.g., cyanoformate and chloroformates [19, 34]), suggest that aldehydes are privileged reagents in this context.
It may be assumed that the oxidation occurs via an intermediate enolate
giving rise to an allylic structure.
Although several synthetic methodologies have been developed to access ketene aminal phosphates, the most convenient strategy consists of the deprotonation of an enolisable ketone using a strong base, such as LDA, followed by reaction of the subsequent metal enolate
with a phosphoryl chloride (Scheme 1).
Combustion fuel additives comprising metal enolates
. US 4 474 580, 1984.
Ian Paterson described the synthesis of complex acyclic and macrocyclic polypropionate derived-natural products based on optimized strategies for stereoselective formation of syn-syn and anti-syn aldol adducts using tin and boron enolates
. High enantioselectivity can also be achieved through the use of chiral borane catalysts to effect aldols starting with acyclic ketones.
The remaining 12 chapters are presented in the same thorough, clearly organized format, with topics that include structural organomanganese chemistry, structures and reaction mechanisms of manganese oxidants, organomangenese-mediated radical reactions, and the chemistry of manganese enolates
. The editors note the omission of manganese-containing photosystem II due to extensive coverage elsewhere.
They also cover nucleic substitution at aliphatic carbon, synthesis of epoxides and aziridines, the protonation of enolates
and kinetic resolution of racemic alcohols and amines.
In the area of methodology, the emphasis is on photocycloaddition-fragmentation reactions, new applications of the Diels-Alder reaction, development of synthetically useful phosphorus-containing reagents, chemical reactivity of Ce(III) enolates
, and synthetic application of thiol esters.