Pd·Et3B-catalyzed alkylation of amines with allylic alcoholsElectronic supplementary information (ESI) available: experimental section. See http://www.rsc.org/suppdata/cc/b2/b210920d/

Kimura, Masanari; Futamata, Makoto; Shibata, Kazufumi; Tamaru, Yoshinao

doi:10.1039/b210920d

Cited by 105 publications

(21 citation statements)

References 8 publications

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“…According to our computational results, the high regio-and stereoselectivity of the catalyst could influence the reactive route of the reaction, which induces different preponderant chiral product. This view could be proved by the high ratio of the chiral products in the experiment (Kimura et al, 2003;Piechaczyk et al, 2006;Banerjee et al, 2014). The high regio-and stereoselectivity is caused by the steric hindrance between the substrate and the ligand.…”

Section: Resultsmentioning

confidence: 87%

Exploring the Mechanism of the Palladium-Catalyzed 3-Butene-2-ol Amination Reaction: A DFT Study

et al. 2020

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Palladium-catalyzed asymmetric allylic substitution, due to its valuable reactive profile, has become a quite useful tool in organic synthesis fields. In the present study, density functional theory (DFT) calculations were applied to investigate the important factors for palladium-catalyzed 3-butene-2-ol and methylaniline amination reaction, with tetrahydrofuran (THF) as solvent. We find that this catalytic protocol results in high regio-and stereoselectivity, which is in line with the experimental result. According to our calculations, the high regio-and stereoselectivity is caused by the steric hindrance between the substrate and the catalyst ligand. To verify this point, we further explore the reactive process with different axial chirality on the catalyst ligand (altering the steric hindrance), and the results suggest that the preponderant R chiral configuration product has reversed. These results could lead to a better understanding of the mechanism for 3-butene-2-ol amination reaction and are helpful for the design of the corresponding catalyst ligand in the industry.

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Section: Resultsmentioning

confidence: 87%

Exploring the Mechanism of the Palladium-Catalyzed 3-Butene-2-ol Amination Reaction: A DFT Study

et al. 2020

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“…[19] The reaction displays remarkable ligand effects: alkylation of aromatic amines is effected by Pd(PPh 3 ) 4 /Et 3 B and is successful for a variety of allyl alcohols (Scheme 11), while the catalyst fails completely in the alkylation of aliphatic amines (Scheme 12). Benzylamine, for example, remained intact under the conditions.…”

Section: Activation Of Allyl Alcohols As Allyl Cationsmentioning

confidence: 99%

Activation of Allyl Alcohols as Allyl Cations, Allyl Anions, and Amphiphilic Allylic Species by Palladium

Tamaru

2005

Eur J Org Chem

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254

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Palladium/Et 3 B induces allyl alcohols to undergo electrophilic allylation of soft carbonucleophiles (pK a 5-14), alkyl aldehydes at the α-position, and amines, indoles, and tryptophan at the 3-position. The same catalyst, and also Pd/Et 2 Zn, also effect the generation of allyl anions from allyl alcohols, which react with aromatic and aliphatic aldehydes and imines to furnish homoallyl alcohols and homoallylamines, respectively, in good yields. 2-Methylenepropane-1,3-diol

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“…Pd‐(π‐allyl) complexes have good catalytic activities but they are not easy to prepare and some of them need water‐ and oxygen‐free operation . Pd(PPh 3 ) 4 , a zero‐valent palladium complex, can successfully catalyze the amination reaction of allylic alcohols with the addition of Et 3 B . Some simple palladium compounds, such as Pd(OAc) 2 and Pd(acac) 2 combined with phosphorus ligands were also used as catalytic systems to achieve good results.…”

Section: Introductionmentioning

confidence: 99%

Palladium‐Catalyzed Direct Amination of Allylic Alcohols in Aqueous Media

Yan

et al. 2016

Asian J Org Chem

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Palladium chloride-catalyzed amination of allylic alcohols with aromatic amines in the presence of triphenylphosphine and trifluoroacetic acid in the aqueous phase gave aw ide range of allylamines in good to excellent yields under mild conditions. This protocol has aw ides ubstrate scope and broad functionalgroup tolerance. It is an environmentally friendly and highly atom-economical method for Nallylamine synthesis. Ap lausible mechanismi nvolving a( pallyl)palladium complex intermediate is proposed.

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Pd·Et3B-catalyzed alkylation of amines with allylic alcoholsElectronic supplementary information (ESI) available: experimental section. See http://www.rsc.org/suppdata/cc/b2/b210920d/

Cited by 105 publications

References 8 publications

Exploring the Mechanism of the Palladium-Catalyzed 3-Butene-2-ol Amination Reaction: A DFT Study

Exploring the Mechanism of the Palladium-Catalyzed 3-Butene-2-ol Amination Reaction: A DFT Study

Activation of Allyl Alcohols as Allyl Cations, Allyl Anions, and Amphiphilic Allylic Species by Palladium

Palladium‐Catalyzed Direct Amination of Allylic Alcohols in Aqueous Media

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