Transition‐Metal‐Catalyzed Hydroamination Reactions

Schafer, Laurel L.; Yim, Jacky C.‐H.; Yonson, Neal

doi:10.1002/9783527655588.ch15

Cited by 31 publications

(27 citation statements)

References 375 publications

(608 reference statements)

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“…In addition, the differences between neutral and anionic nucleophiles, and between N - and O -nucleophiles are also explored. In agreement with previous experimental observations, 1c,4a,4b most of the nucleophiles investigated favor Markovnikov-selective nucleopalladation. Surprisingly, the EDA results indicate that the kinetic regioselectivity of nucleopalladation is not very sensitive to the steric properties of the nucleophile.…”

Section: Resultssupporting

confidence: 92%

“…This conclusion is consistent with previous mechanistic studies that suggest reactions with strongly coordinating nucleophiles prefer the cis -nucleopalladation. 1c,10a…”

Section: Resultsmentioning

confidence: 99%

“…Palladium-catalyzed hydro- and oxidative functionalization of unactivated aliphatic alkenes is an efficient and atom-economical synthetic strategy for new C‒C and C‒heteroatom bond formation. 1 One of the most common mechanistic pathways in these reactions involve nucleopalladation, in which a nucleophilic coupling partner attacks a π-alkene-Pd complex via either syn -insertion or anti -attack (also referred to as cis - and trans -nucleopalladation, respectively). 2 Controlling the regioselectivity still remains a significant challenge in intermolecular nucleopalladation with sterically and electronically unbiased aliphatic alkenes.…”

Section: Introductionmentioning

confidence: 99%

“…8 In contrast, computational studies on the regioselective nucleopalladation of alkenes are limited due to the complexity of regioselectivity control. 9 The potential competition between cis - and trans -nucleopalladation pathways 1c,10 further complicated the computational analysis (Figure 1a). Here, we present a systematic computational approach to quantitatively analyze the contributions of different types of effects to the regioselectivity in cis - and trans -nucleopalladations with different palladium catalysts and a variety of N - and O -nucleophiles with different formal charges, steric hinderances, and nucleophilicities (Figure 1c).…”

Section: Introductionmentioning

confidence: 99%

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Energy Decomposition Analyses Reveal the Origins of Catalyst and Nucleophile Effects on Regioselectivity in Nucleopalladation of Alkenes

Kohler

Hull

et al. 2019

J. Am. Chem. Soc.

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Nucleopalladation is one of the most common mechanisms for Pd-catalyzed hydro- and oxidative functionalization of alkenes. Due to the electronic bias of the π-alkene-palladium complexes, nucleopalladations with terminal aliphatic alkenes typically deliver the nucleophile to the more substituted sp2 carbon to form the Markovnikov-selective products. The selective formation of the anti-Markovnikov nucleopalladation products requires the inherent electronic effects to be overridden, which is still a significant challenge for reactions with simple aliphatic alkenes. Because the interactions between the nucleophile and the alkene substrate are influenced by a complex combination of multiple types of steric and electronic effects, a thorough understanding of the interplay of these underlying interactions is needed to rationalize and predict the regioselectivity. Here, we employ an energy decomposition approach to quantitatively separate the different types of nucleophile-substrate interactions, including steric, electrostatic, orbital interactions, and dispersion effects, and to predict the impacts of each factor on regioselectivity. We demonstrate the use of this approach on the origins of catalyst-controlled anti-Markovnikov-selectivity in Hull’s Pd-catalyzed oxidative amination reactions. In addition, we evaluated the regioselectivity in a series of nucleopalladation reactions with different neutral and anionic Pd catalysts and N- and O-nucleophiles with different steric and electronic properties. Based on these computational analyses, a generalized scheme is established to identify the dominant nucleophile-substrate interaction affecting the regioselectivity of nucleopalladations with different Pd catalysts and nucleophiles.

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Section: Resultssupporting

confidence: 92%

“…This conclusion is consistent with previous mechanistic studies that suggest reactions with strongly coordinating nucleophiles prefer the cis -nucleopalladation. 1c,10a…”

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Energy Decomposition Analyses Reveal the Origins of Catalyst and Nucleophile Effects on Regioselectivity in Nucleopalladation of Alkenes

Kohler

Hull

et al. 2019

J. Am. Chem. Soc.

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“…[3] When an alkynei sr eacted with ap rimary amine in this manner,c onjugated secondary enamines can be prepared. These reactionsr esult in the addition of an NÀHb ond across an unsaturatedC ÀCb ond, and can proceedu nder mild conditions with appropriate catalysts.…”

Section: Introductionmentioning

confidence: 99%

Ti‐Catalyzed Hydroamination for the Synthesis of Amine‐Containing π‐Conjugated Materials

Han

Thompson

Hudson

et al. 2018

Chemistry A European J

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A series of conjugated enamines were prepared by Ti catalyzed anti-Markovnikov hydroamination. The synthetic route is efficient with yields of up to 94 % and the 100 % atom efficiency of the reaction means that these products are easily isolated and purified. Due to the extended conjugated system, the enamine tautomers were observed exclusively in both solid and solution phases, as determined by X-ray crystallography and NMR spectroscopy. These new conjugated molecules, with N incorporated into the backbone, show interesting photophysical properties including photo-luminescent quantum yields of up to 0.26. Notably, through the incorporation of B to give a donor-acceptor π-conjugated system, a redshift of approximately 100 nm is observed for the emission maximum along with the anticipated solvatochromic shifts.

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Facile Synthesis and Isolation of Secondary Amines via a Sequential Titanium(IV)‐Catalyzed Hydroamination and Palladium‐Catalyzed Hydrogenation

Lui

Schafer

2016

Adv Synth Catal

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An atom economical and catalytic route for the synthesis of aryl‐ and alkyl‐substituted secondary amines has been developed. Using a bis(amidate)bis(amido)titanium(IV) precatalyst, the hydroamination of terminal alkynes with a range of amines results in the selective formation of the anti‐Markovnikov product. The crude enamine/imine mixtures are effectively hydrogenated using palladium on carbon (Pd/C) and H2 to afford the corresponding secondary amine in excellent yields. Simple work‐up procedures allow for the isolation of pure compounds while avoiding purification via column chromatography.magnified image

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Transition‐Metal‐Catalyzed Hydroamination Reactions

Cited by 31 publications

References 375 publications

Energy Decomposition Analyses Reveal the Origins of Catalyst and Nucleophile Effects on Regioselectivity in Nucleopalladation of Alkenes

Energy Decomposition Analyses Reveal the Origins of Catalyst and Nucleophile Effects on Regioselectivity in Nucleopalladation of Alkenes

Ti‐Catalyzed Hydroamination for the Synthesis of Amine‐Containing π‐Conjugated Materials

Facile Synthesis and Isolation of Secondary Amines via a Sequential Titanium(IV)‐Catalyzed Hydroamination and Palladium‐Catalyzed Hydrogenation

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