The difluoroalkylation of alkynes and alkenes by direct
photoexcitation
of ethyl difluoroiodoacetate is described. Under catalyst- and oxidant-free
conditions, iododifluoroalkylation and hydrodifluoroalkylation
products were generated from alkynes, and difluoroalkylation products
were prepared from alkenes. This methodology provides a streamlined
access to difluoroalkylated organic compounds starting from simple
alkynes or alkenes.
A facile and cost-effective
method for the preparation of fluoroalkylated
compounds has been described by the direct photoexcitation of halofluoroalkanes
with blue light absorptivity, enabling the difluoroalkylation of aryl
ketones. The methodology has provided an efficient, mild, and catalyst-free
synthetic method for quaternary difluoroalkylated arenes and tetrasubstituted
monofluoroalkenes.
An
efficient method for the directing group controlled rhodium-catalyzed
addition reaction of oxa/azabicylic alkenes with aromatic ketones
and benzoic acids has been developed. The ketones and benzoic acids
afforded different addition products when reacted with oxa/azabicyclic
alkenes. The reaction between ketones and azabenzonorbornadienes furnished
the ring-opening addition products. The reaction between benzoic acids
and aza/oxabicyclic alkenes proceeded in the absence of silver salt,
giving the 1:2 hydroarylation products in yields up to 96%.
A Co-catalyzed effective transfer hydrogenation of various α-ketoesters and N-cyclicsulfonylimides by safe and environmentally benign H 2 O as hydrogen source is described. The reaction used easily available and easy to handle zinc metal as a reductant. Interestingly, the catalytic system does not require ligand for reduction of N-cyclicsulfonylimides.
An
efficient, catalyst/photocatalyst-free, and cost-effective methodology
for the decarboxylative alkylation of α,β-unsaturated carboxylic acids to synthesize β,γ-unsaturated nitriles has
been developed. The reaction proceeded in an environmentally benign
atmosphere of blue light-emitting diode irradiation with K2CO3 and water at room temperature. The methodology worked
for a wide range of substrates (22 examples) with up to 83% yield.
The protocol is also compatible for gram-scale synthesis.
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