Categories: C-C Bond Formation > Oxygen-containing molecules > Carbonyl compounds >
Synthesis of substituted carbonyl compounds by 1,4-additions
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Tin-free Giese reaction of alkyl iodides with electron-deficient alkenes and the
related radical carbonylation process proceeded efficiently in the presence of
sodium cyanoborohydride and tetrabutylammonium cyanoborohydride. Transfer of
iodine followed by hydride reduction of the resulting carbon-iodine bond is
proposed as a possible mechanism.
I. Ryu, S. Uehara, H. Hirao, T. Fukuyama, Org. Lett., 2008,
10, 1005-1008.
Conjugated aldehydes undergo smooth 1,4-addition of dialkylzinc reagents
under Pd or Cu catalysis.
J. A. Marshall, M. Herold, H. S. Eidam, P. Eidam, Org. Lett., 2006,
8, 5505-5508.
A new tridentate alanine-derived aminohydroxyphosphine ligand induces
consistently high enantioselectivity in copper-catalyzed asymmetric
conjugate additions of organozinc reagents to various acyclic enones. A
highly ordered transition state is proposed.
A. Hajra, N. Yoshikai, E. Nakamura, Org. Lett.,
2006,
8, 4153-4155.
A highly enantioselective addition of Grignard reagents to
acyclic aliphatic enones provides β-substituted linear ketones with high yields, regio-, and
enantioselectivities in the presence of 5 mol % of CuBr·SMe2 and
6 mol % of JosiPhos diphosphine.
F. López, S. R. Harutyunyan, A. J. Minnaard, B. L. Feringa, J. Am. Chem. Soc.,
2004,
126, 12784-12785.
A new P-chiral phosphine bis(sulfonamide) ligand allows the Cu-catalyzed
enantioselective conjugate addition of Et2Zn to various acyclic
aliphatic enones with excellent levels of enantioselectivity at
ambient temperature.
A. P. Duncan, J. L. Leighton, Org. Lett., 2004, 6,
4117-4119.
A new, readily to prepare, air-stable, crystalline ligand for Cu-catalyzed
enantioselective additions of dialkylzincs to cyclic enones provides optimal performance (good to excellent
enantioselectivities) at ambient temperature with a range of substrates.
I. J. Krauss, J. L. Leighton, Org. Lett., 2003,
5, 3201-3203.
The 1,4-addition of dialkylzincs to cyclic enones proceeded with ee values
up to 99% by using chiral aryl diphosphite ligands derived from H8-binaphthol.
L. Liang, T. T.-L. Au-Yeung, A. S. C. Chan, Org. Lett., 2002,
4, 3799-3801.
An efficient and practical Cu-catalyzed asymmetric conjugate addition of
dialkylzinc reagents to tetrasubstituted cyclic enones afforded quaternary
all-carbon stereogenic centers in up to 95% ee. The products can be readily
functionalized to afford various synthetically versatile compounds in high
optical purity.
A. W. Hird, A. H. Hoveyda, J. Am. Chem. Soc.,
2005,
127, 14988-14989.
Cu-catalyzed enantioselective conjugate additions of alkyl- and arylzinc
reagents to unactivated cyclic β-substituted enones are promoted in the
presence of 2.5-15 mol% of a readily available chiral NHC-based Cu complex,
affording the desired products bearing all-carbon quaternary stereogenic
centers in good yield and enantioselectivity.
K.-S. Lee, M. K. Brown, A. W. Hird, A. H. Hoveyda, J. Am. Chem. Soc.,
2006,
128, 7182-7184.
An additive-free, clean conjugate addition reaction of organosiloxanes to α,β-unsaturated
compounds is catalyzed by a cationic rhodium complex in dioxane/water. The
mechanism involves a transmetalation step between the rhodium complex and the
silicon reagent.
S. Oi, Y. Honma, Y. Inoue, Org. Lett., 2002,
4, 667-669.
A conjugate addition of organosiloxanes to α,β-unsaturated carbonyl
compounds catalyzed by a cationic rhodium complex generated from [Rh(cod)(MeCN)2]BF4
and (S)-BINAP in dioxane/water gave products in good yields and excellent
enantioselectivities.
S. Oi, A. Taira, Y. Honma, Y. Inoue, Org. Lett.,
2003, 5, 97-99.
C2-symmetric chiral diene ligands based on a 3,7-disubstituted
bicyclo[3.3.1]nona-2,6-diene readily bind to rhodium(I). These rhodium complexes
act as effective catalysts for 1,4-addition of alkenyl- and arylboronic acids to
various α,β-unsaturated ketones, including several combinations that were
previously difficult to provide high enantioselectivity.
R. Shintani, Y. Ichikawa, K. Takatsu, F.-X. Chen, T. Hayashi, J. Org. Chem., 2009,
74, 869-873.
A chiral diene possessing the bicyclo[2.2.2]octadiene framework substituted with
a tertiary alcohol on one of the two double bonds is readily prepared in two
steps and is highly effective as a chiral ligand for rhodium-catalyzed
asymmetric conjugate addition reactions, giving the corresponding addition
products with high enantioselectivity.
K. Okamoto, T. Hayashi, V. H. Rawal, Org. Lett.,
2008,
10, 4387-4389.
The use of unsaturated methylidene ketones in catalytic conjugate allylations
allows a significant expansion in substrate scope and occurs in a highly
enantioselective fashion in the presence of a Taddol-derived phosphinite ligand.
L. A. Brozek, J. D. Sieber, J. P. Morken, Org. Lett., 2011,
13, 995-997.
Conjugate addition of dimethyl alkenylboronates to α,β-unsaturated ketones in the presence of catalytic amounts of 3,3'-disubstituted binaphthols provides alkenylation products in good yields and
high enantioselectivities.
T. R. Wu, J. M. Chong, J. Am. Chem. Soc., 2007,
129, 4908-4909.
A direct conjugate addition of simple alkenes to enones has been achieved in
the presence of a Ni(0)/PCy3 catalyst. This reaction is a
straightforward method for the introduction of an alkenyl group at the
β-position of enones.
S. Ogoshi, T. Haba, M. Ohashi, J. Am. Chem. Soc., 2009,
131, 10350-10351.
Cobalt complex/Zn systems effectively catalyze the reductive coupling of
activated alkenes with alkynes in the presence of water to give substituted
alkenes with very high regio- and stereoselectivity in excellent yields.
H.-T. Chang, T. T. Jayanth, C.-C. Wang, C.-H. Cheng, J. Am. Chem. Soc.,
2007,
129, 12032-12041.
Reductive coupling of enones or enals with alkynes using reducing agents such
as organozincs, organoboranes, organosilanes, and methanol is cost-effective,
and tolerant of many functional groups. Isotopic labeling strategies have
provided supporting evidence for the mechanistic proposals.
W. Li, A. Herath, J. Montgomery, J. Am. Chem. Soc., 2009,
131, 17024-17029.
A nickel-catalyzed intermolecular reductive coupling of enones and alkynes
gives γ,δ-unsaturated ketones. The process does not require formation of a vinyl
organometallic, and a variety of functional groups including free hydroxyls and
esters are tolerated.
A. Herath, B. B. Thompson, J. Montgomery, J. Am. Chem. Soc., 2007,
129, 8712-8713.
A three-component nickel-catalyzed coupling of enals, alkynes, and silanes forms
an enol silane and a trisubstituted alkene with >98:2 stereoselectivity. The
reaction tolerates a broad range of functionality including aldehydes, ketones,
esters, free hydroxyls, and basic secondary amines.
A. Herath, J. Montgomery, J. Am. Chem. Soc., 2008,
130, 8132-8133.
A rapid and simple conjugate alkynylation of acyclic enones using sp-hybridised
potassium organotrifluoroborates in the presence of BF3•OEt2
is suitable for the preparation of small compound libraries.
F. Bertolini, S. Woodward, Synlett, 2009,
51-54.
An asymmetric 1,3-rearrangement of an alkynyl group of alkynyl alkenyl carbinols
took place in the presence of a hydroxyrhodium/(R)-binap catalyst to
yield β-alkynylketones in high yields with high enantioselectivity. The present
method includes a key β-alkynyl elimination step in the catalytic cycle.
T. Nishimura, T. Katoh, K. Takatshu, R. Shintani, T. Hayashi, J. Am. Chem. Soc., 2007,
129, 14158-14159.
Efficient Addition of Allylsilanes to α,β-Enones Using Catalytic Indium and
Trimethylsilyl Chloride
P. H. Lee, D. Seomoon, S. Kim, K. Nagaiah, S. V. Damle, K. Lee, Synthesis,
2003, 2023-2026.
The C2-symmetric norbornadiene derivative (1R,4R)-2,5-dibenzylbicyclo[2.2.1]hepta-2,5-diene
was used as ligand for the rhodium-catalyzed asymmetric 1,4-addition of
organoboron and -tin reagents to α,β-unsaturated ketones, which gave high
yields of the addition products with up to 99% enantioselectivity.
T. Hayashi, K. Ueyama, N. Tokunaga, K. Yoshida, J. Am. Chem. Soc.,
2003,
125, 11508-11509.
Gd(OTf)3 as co-catalyst dramatically accelerated a Ni-catalyzed
conjugate addition of cyanide to enones. The substrate scope of the reaction is
broad, including cyclic, linear, branched, and aromatic enones. Gadolinium
triflate is supposed to facilitate the oxidative addition of Ni(0) to enones,
which constitutes a key step in the catalytic cycle.
Y. Tanaka, M. Kanai, M. Shibasaki, Synlett, 2008, 2295-2298.
A catalytic enantioselective direct conjugate addition of nitroalkanes to
α,β-unsaturated aldehydes using diphenylprolinol silyl ether as an
organocatalyst enables short syntheses of therapeutically useful compounds.
H. Gotoh, H. Ishikawa, Y. Hayashi, Org. Lett., 2007,
9, 5307-5309.
An N-spiro C2-symmetric chiral quaternary ammonium
bromide efficiently catalyzed the conjugate addition of various prochiral
nitroalkanes to cyclic α,β-unsaturated ketones under solid-liquid
phase-transfer conditions to afford the corresponding γ-nitro ketones in
excellent yields with high levels of diastereo- and enantiocontrol.
T. Ooi, S. Takada, S. Fujioka, K. Maruoka, Org. Lett.,
2005,
7, 5143-5146.
