Categories: C-C Bond Formation > Oxygen-containing molecules > Carbonyl compounds >
Synthesis of allyl ketones and aldehydes
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A selective coupling of alkynylsilanes and allyltrimethylsilane is catalyzed
by 5 mol% of indium tribromide under mild conditions to afford the
corresponding α,β-acetylenic ketones and β,γ-unsaturated ketones in
excellent yields.
J. S. Yadav, B. V. S. Reddy, M. Sridhar Reddy, G. Parimala, Synthesis,
2003, 2390-2394.
A dual Ni/photoredox system was successfully employed to generate acyl
radicals from aldehydes via selective formyl C-H activation. A subsequently
cross-coupling with benzylic and allylic pyridinium salts provides ketones. The
reaction tolerates a broad range of functional groups.
V. Murugesan, A. Ganguly, A. Karthika, R. Rasappan, Org. Lett., 2021, 23,
5389-5393.
A highly regio- and enantioselective copper-catalyzed three-component coupling
of isocyanides, hydrosilanes, and γ,γ-disubstituted allylic phosphates/chlorides
provides chiral α-quaternary formimides in the presence of a chiral
naphthol-carbene ligand and LiOtBu as base. The formimides can readily be
converted to α-quaternary aldehydes.
K. Hojoh, H. Ohmiya, M. Sawamura, J. Am. Chem. Soc., 2017,
139, 2184-2187.
A Cu-catalyzed hydroalumination of readily accessible allenes with
diisobutylaluminum hydride provides allylaluminum reagents under mild
reaction conditions. A subsequent tandem nucleophilic addition to
aldehydes/Oppenauer oxidation enables a
one-pot synthesis of allylic ketones with α-tertiary and α-quaternary centers.
S. Lee, S. Lee, Y. Lee,
Org. Lett., 2020, 22, 5806-5810.
Substituted allylic zinc reagents, prepared via direct metal insertion in
substituted allylic halides, react readily with a broad range of acid chlorides
and chloroformates to yield the corresponding α-substituted β,γ-unsaturated
ketones and esters in high yield and perfect regioselectivity.
C. Sämann, P. Knochel, Synthesis, 2013, 45,
1870-1876.
A nickel/photo-cocatalyzed C(sp2)-H allylation of aldehydes and
formamides with allyl acetates or allyl alcohols provides various
β,γ-unsaturated ketones and amides with high selectivities. Tetrabutylammonium
decatungstate catalyzes a radical-type umpolung of the formyl moiety, whereas
nickel cleaves the C-O bond of allyl acetates or allyl alcohols.
P. Fan, R. Wang, C. Wang, Org. Lett., 2021, 23,
7672-7677.
Tandem Ru-catalysis enables the coupling of internal alkynes with aldehydes for
the synthesis of β,γ-unsaturated ketones with high regioselectivity. The
catalyst for example differentiates between methyl and ethyl substituent on the
alkyne.
Q.-A. Chen, F. A. Cruz, V. M. Dong, J. Am. Chem. Soc., 2015,
137, 3157-3160.
A cobalt-catalyzed hydroacylation of 1,3-dienes with non-chelating aromatic
aldehydes provides 1,4-addition products as the major isomer, while aliphatic
aldehydes favor 1,2-hydroacylation products. The kinetic profile supports an
oxidative cyclization mechanism involving a cobaltacycle intermediate that
undergoes transformation with high regio- and stereoselectivity.
Q.-A. Chen, D. K. Kim, V. M. Dong, J. Am. Chem. Soc., 2014,
136, 3772-3775.
Under the conditions of ruthenium-catalyzed transfer hydrogenation, 1,3-dienes
couple to benzylic and aliphatic alcohols and aldehydes to deliver
β,γ-unsaturated ketones in very good yields. In all cases, complete branch
regioselectivity is observed.
F. Shibahara, J. F. Bower, M. J. Krische, J. Am. Chem. Soc., 2008,
130, 14120-14122.
F. Shibahara, J. F. Bower, M. J. Krische, J. Am. Chem. Soc., 2008,
130, 14120-14122.
An efficient cross-addition reaction of dienes with aldehydes in the presence of
RuHCl(CO)(PPh3)3 as catalyst gives various β,γ-unsaturated
ketones. A π-allylruthenium species, derived from hydroruthenation of the diene,
may be involved as a key intermediate.
S. Omura, T. Fukuyama, J. Horiguchi, Y. Murakami, I. Ryu, J. Am. Chem. Soc., 2008,
130, 14094-14095.
Commercially available chiral ligands enable a widely applicable, practical,
and scalable strategy for efficient and enantioselective synthesis of
β,γ-unsaturated ketones that contain an α-stereogenic center.
J. del Pozo, S. Zhang, F. Romiti, S. Xu, R. P. Conger, A. H. Hoveyda, J. Am. Chem. Soc.,
2020, 142, 18200-18212.
An efficient, practical photocatalytic deoxygenation/defluorination protocol
provides γ,γ-difluoroallylic ketones from commercially available aromatic
carboxylic acids and α-trifluoromethyl alkenes in the presence of
triphenylphosphine. The protocol offers good functional group tolerance and a
broad substrate scope.
Y.-Q. Guo, R. Wang, H. Song, Y. Liu, Q. Wang,
Org. Lett., 2020, 22, 709-713.