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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 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.

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]₂and 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 L_naph 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.