Categories: C-C Bond Formation > Oxygen-containing molecules > Carbonyl compounds >
Synthesis of substituted carbonyl compounds by 1,4-Additions
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Recent Literature
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 (90-95% ee) 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 has
been developed. This ligand provides optimal performance (good to excellent
enantioselectivities) at ambient temperature with a range of cyclic enones
and dialkylzincs.
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.
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.
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.
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.
