Categories: C-C Bond Formation > Oxygen-containing molecules > Carbonyl compounds >
Allylations
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A simple method for the chemo- and regioselective, direct catalytic allylic alkylation of aldehydes and cyclic ketones has been developed. The combination of palladium and enamine catalysis furnished α-allylic alkylated aldehydes and cyclic ketones in high yields.
I. Ibrahem, A. Córdova, Angew. Chem. Int. Ed., 2006, 45, 1952-1956.
A simple method for the chemo- and regioselective, direct catalytic allylic
alkylation of aldehydes and cyclic ketones has been developed. The
combination of palladium and enamine catalysis furnished α-allylic alkylated
aldehydes and cyclic ketones in high yields.
I. Ibrahem, A. Córdova, Angew. Chem. Int. Ed., 2006,
45, 1952-1956.
A chiral primary amino acid organocatalyst mediates an enantioselective
α-allylation and -propargylation of α-branched aldehydes with alkyl halides in a
good yield and high enantioselectivity to furnish α-allylated or -propargylated
aldehydes with chiral quaternary carbon stereocenters. The reaction proceeded
smoothly in a mildly basic aqueous solution of potassium hydrogen carbonate.
M. Yoshida, J. Org. Chem., 2021, 86,
10921-10927.
A straightforward and efficient Pd/enamine catalytic procedure enables the
direct asymmetric α-allylation of branched aldehydes with different allylic
alcohols in the presence of a simple chiral amine and an easily prepared achiral
or racemic phosphoric acid.
Á. M. Pálvölgyi, J. Smith, M. Schnürch, K. Bica-Schröder, J. Org. Chem., 2021, 86,
850-860.
Iridium- and amine-catalyzed substitution of racemic allylic alcohols enables a
highly enantioselective α-allylation of acetaldehyde. The method utilizes
an aqueous
solution of acetaldehyde and furnishes γ,δ-unsaturated aldehydes in good yields.
T. Sandmeier, E. M. Carreira,
Org. Lett., 2020, 22, 1135-1138.
A highly enantioselective Pd/chiral acid-catalyzed α-allylation of α-branched
aldehydes with an allyl amine as the allylating species creates all-carbon
quaternary stereogenic centers in high yields and enantioselectivities.
S. Mukherjee, B. List, J. Am. Chem. Soc.,
2007,
129, 11336-11337.
A highly enantioselective rhodium-catalyzed allylic alkylation of prochiral
α,α-disubstituted aldehyde enolates with allyl benzoate provides acyclic
quaternary carbon stereogenic centers.
T. B. Wright, P. A. Evans, J. Am. Chem. Soc., 2016,
138, 15303-15306.
A Rh-bisoxazolinephosphine system catalyzes a highly branch-selective and
enantioselective allylic alkylation of simple ketones with racemic aliphatic
allylic carbonates under mild conditions to provide a series of chiral
β-branched γ,δ-unsaturated ketones with excellent regio- and
enantioselectivities.
B. Li, C. Li, Synlett, 2022,
33,
1863-1867.
An enantioselective Pd-catalyzed decarboxylative allylic
alkylation of fully substituted acyclic enol carbonates provides linear
α-quaternary ketones. The use of an electron-deficient phosphinooxazoline ligand renders the enolate
geometry of the starting material inconsequential, with the same enantiomer of
product obtained in the same level of selectivity regardless of the starting
ratio of enolates.
E. J. Alexy, H. Zhang, B. M. Stoltz, J. Am. Chem. Soc.,
2018,
140, 10109-10112.
A copper-catalyzed cross-coupling of substituted allylboronic acids with
α-diazoketones is highly regioselective, providing the branched allylic product.
The process involves creation of a new C(sp3)–C(sp3) bond
by retaining the keto functional group of the α-diazoketone precursor.
A. Das, D. Wang, M.-C. Belhomme, K. J. Szabo, Org. Lett.,
2015,
17, 4754-4757.
Hydrogen-bond-activated C-N bond cleavage enables Pd-catalyzed allylic
alkylation of allylic amines with carbonyl compounds in inexpensive methanol as
solvent. The method allows the conversion of a series of allylic amines and
carbonyl compounds with excellent results.
X. Zhao, D. Liu, H. Guo, Y. Liu, W. Zhang, J. Am. Chem. Soc., 2011,
133, 19354-19357.
A fully stereodivergent, dual catalytic α-allylation of linear aldehydes
proceeds via direct iridium-catalyzed substitution of racemic allylic alcohols
with enamines generated in situ. The use of an Ir(P,olefin) complex and a
diarylsilyl prolinol ether as catalysts in the presence of dimethylhydrogen
phosphate as the promoter is crucial for achieving high enantio- and
diastereoselectivity.
S. Krautwald, M. A. Schafroth, D. Sarlah, E. M. Carreira, J. Am. Chem. Soc., 2014,
136, 3020-3023.
Iridium complexes catalyze a conversion of allyl homoallyl ethers to
γ,δ-unsaturated carbonyl compounds in toluene at 100°C. The reaction proceeds
through double bond migration to allyl vinyl ethers, which then undergo the
Claisen rearrangement.
T. Higashino, S. Sakaguchi, Y. Ishii,
Org. Lett., 2000, 2, 4193-4195.
Cyclopentanone as an electron pair donor proved highly efficient for the
stabilization of allyl and vinyl cations in combination with a calcium-based
catalyst system. The system enabled a transition-metal-free intermolecular
carbohydroxylation of alkynes with allyl and propargyl alcohols.
T. Stopka, M. Niggemann, Org. Lett.,
2015,
17, 1437-1440.
A highly regioselective addition of 1,3-dienes to simple
ketones in the presence of a nickel-hydride catalyst bearing a DTBM-SegPhos ligand provides
synthetically useful γ,δ-unsaturated ketones in high yield and regioselectivity.
An asymmetric version of the reaction was also realized in high
enantioselectivity by using (S)-DTBM-HO-BIPHEP as chiral ligand.
L. Cheng, M.-M. Li, L.-J. Xiao, J.-H. Xie, Q.-L. Zhou, J. Am. Chem. Soc.,
2018,
140, 11627-11630.
A Rh(I)/DPPF system enables a chemo- and regioselective intermolecular
decarboxylative addition of β-ketoacids to terminal allenes, in which tertiary
and quaternary carbon centers were formed with exclusively branched selectivity
under mild conditions. Preliminary mechanism studies support that the
decarboxylation follows the carbon-carbon bond formation and the reaction occurs
in an outer-sphere mechanism.
C. Li, B. Breit, J. Am. Chem. Soc., 2014,
136, 650-652.
A combination of [Ir(COD)Cl]2 and a phosphoramidite ligand is an
efficient catalytic system for a highly regio- and enantioselective
decarboxylative alkylation of γ-substituted allyl β-ketocarboxylates, affording
branched products with a regioselectivity of up to 99:1 and 96% ee.
H. He, X.-J. Zheng, Y. Li, L.-X. Dai, S.-L. You, Org. Lett., 2007,
9, 4339-4341.
In the “deacylative allylation”, the coupling partners, ketone pronucleophiles
and readily available allylic alcohols undergo in situ retro-Claisen activation
to generate an allylic acetate and a carbanion. In the presence of palladium,
these reactive intermediates undergo catalytic coupling to form a new C-C bond.
A. J. Grenning, J. A. Tunge, J. Am. Chem. Soc., 2011,
133, 14785-14794.
An unprecedented asymmetric aza-Claisen rearrangement between enantioenriched
α-chiral allylamines and allenones provides - followed by hydrolysis -
structurally diverse δ-chiral β-diketones in good to excellent yields with
excellent retention of enantiopurity. This protocol enabled the construction of
an all-carbon quaternary stereocenter with high enantiopurity.
R.-H. Dai, Q. Wang, Z.-X. Chen, S.-K. Tian, J. Org. Chem., 2021, 86,
3065-3073.
Catalytic enantioselective examples of the Tsuji allylation using enol
carbonates and enol silanes gave products possessing a quaternary stereogenic
center, which are useful building blocks for synthetic chemistry.
D. C. Behenna, B. M. Stoltz, J. Am. Chem. Soc.,
2004,
126, 15044-15045.
D. C. Behenna, B. M. Stotz, J. Am. Chem. Soc.,
2004,
126, 15044-15045.
A catalytic enantioconvergent synthesis of quaternary stereocenters from
racemates with quaternary stereocenters has been developed. A chiral Pd
catalyst is involved in both the stereoablative (C-C bond-breaking) and
stereoselective (C-C bond-forming) steps.
J. T. Mohr, D. C. Behenna, A. M. Harned, B. M. Stoltz, Angew. Chem. Int.
Ed., 2005,
44, 6924-6927.
The palladium catalyzed decarboxylative asymmetric allylic alkylation of allyl
1,2-enediol carbonates gives exclusively α-hydroxyketones in very good yields
and high enantiomeric excesses using Lnaph as ligand in DME. The
reaction proceeds under extremely mild conditions and tolerates a broad range of
esters.
B. M. Trost, J. Xu, T. Schmidt, J. Am. Chem. Soc., 2008,
130, 11852-11853.
In a new, efficient, catalytic asymmetric protocol for the synthesis of
α-tertiary hydroxyaldehydes from readily available α-halo or α-hydroxy ketones
or enol silyl ethers, the chiral ligand controls the regioselectivity as well as
the enantioselectivity.
B. M. Trost, J. Xu, M. Reichle, J. Am. Chem. Soc., 2007,
129, 282-283.
Cooperative catalysis
of a chiral Pd(0) catalyst and a chiral Brønsted acid enables an asymmetric regioselective asymmetric
α-pentadienylation reaction of aldehydes with cyclopropylacetylene derivatives
as pentadienylation reagents to afford. α-pentadienylated aldehydes in high yields and enantioselectivities as well as excellent
E/Z ratios.
M.-S. Wu, Z.-Y. Han, L.-Z. Gong, Org. Lett., 2021, 23,
636-641.
A combination of chiral hydridopalladium and enamine catalysis enables an
asymmetric α-allylation of aldehydes with alkynes. The ternary catalyst system,
consisting of an achiral palladium complex, a primary amine, and a chiral
phosphoric acid tolerates a wide scope of α,α-disubstituted aldehydes and
alkynes and provides the corresponding allylation products in high yields and
with excellent levels of enantioselectivity.
Y.-L. Su, L-L. Li, X.-L. Zhou, Z.-Y. Dai, P.-S. Wang, L.-Z. Gong, Org. Lett.,
2018, 20, 2403-2406.
Stereodefined enol derivatives of aldehydes are prepared from terminal alkynes
through Cp2ZrCl2-catalyzed methylalumination and
subsequent oxygenation with peroxyzinc species and electrophilic trapping with
carboxylic anydrides. The tandem carbometalation/oxygenation tolerates free and
protected alcohols, heterocycles, olefins, and nitriles.
J. R. DeBergh, K. M. Spivey, J. M. Ready, J. Am. Chem. Soc., 2008,
130, 7828-7829.