The effect of neighborhood density on visual word recognition was found to be facilitatory for words but inhibitory for nonwords in 3 lexical-decision experiments. However, the facilitation virtually disappeared when the task was changed to semantic categorization (animal vs. nonanimal), despite the presence of a strong frequency effect. None of these experiments showed a consistent inhibitory effect of a higher frequency neighbor. The absence of inhibitory effects suggests that competition does not play a key role in visual word recognition. The data also suggest that the neighborhood density effect is not an access effect but is a task-dependent effect instead.
The rhodium-catalyzed methylation of ketones has been accomplished using methanol as the methylating agent and the hydrogen-borrowing method. The sequence is notable for the relatively low temperatures that are required and for the ability of the reaction system to form α-branched products with ease. Doubly alkylated ketones can be prepared from methyl ketones and two different alcohols by using a sequential one-pot iridium- and rhodium-catalyzed process.
Axially chiral biaryl
scaffolds are essential structural units
in chemistry. The asymmetric Pd-catalyzed Suzuki–Miyaura cross-coupling
reaction has been widely recognized as one of the most practical methods
for constructing atropisomers of biaryls. However, longstanding challenges
remain in this field. For example, substrate scope is often narrow
and specialized, functional groups and heterocycles can lead to reduced
reactivity and selectivity, bulky ortho-substituents
are usually needed, and reported methods are generally inapplicable
to tetra-ortho-substituted biaryls. We have developed
an unprecedented highly enantioselective N-heterocyclic carbene (NHC)-Pd
catalyzed Suzuki–Miyaura cross-coupling reaction for the synthesis
of atropisomeric biaryls. These reactions enable efficient coupling
of aryl halides (Br, Cl) or aryl triflates with various types of aryl
boron compounds (B(OH)2, Bpin, Bneo, BF3K),
tolerate a remarkably broad scope of functional groups and heterocycles
(>41 examples), employ low loading of catalyst (0.2–2 mol
%),
and proceed under mild conditions. The protocol provided general and
efficient access to various atropisomeric biaryls and heterobiaryls
in excellent enantioselectivities (up to 99% ee) with no need
of using bulky ortho-substituted substrates and was
effective for the synthesis of tetra-ortho-substituent
biaryls. Moreover, the method was successfully applied to the diastereo-
and enantioselective synthesis of atropisomeric ternaphthalenes. Critical
to the success of the reaction is the development and application
of an extremely bulky C
2-symmetric chiral
NHC, (R,R,R,R)-DTB-SIPE, as the ligand for palladium. To the best of
our knowledge, this is the first highly enantioselective (>90%
ee)
example of a chiral NHC-metal-catalyzed C(sp2)–C(sp2) cross-coupling reaction.
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