Palladium-catalyzed additions of amines to conjugated dienes. Alteration of behavior of triphenylphosphine-palladium catalysts with amine hydroiodide salts

Armbruster, Robert; Morgan, Michael M.; Schmidt, James L.; Lau, Chun M.; Riley, Rose M.; Zabrowsky, Daniel L.; Dieck, Harold A.

doi:10.1021/om00133a011

Cited by 46 publications

(13 citation statements)

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“…Building upon this observation, in an effort to probe aspects of overall reaction reversibility and the reversibility of individual steps of the catalytic cycle, we carried out a series of experiments. As a framework for discussion, a proposed catalytic cycle for the internal diene hydroamination is shown in Scheme . After initiation of Pd-1 , coordination of diene 1a to Pd 0 –PHOX affords intermediate i .…”

Section: Resultsmentioning

confidence: 99%

Development and Mechanistic Investigations of Enantioselective Pd-Catalyzed Intermolecular Hydroaminations of Internal Dienes

Park

Malcolmson

2018

ACS Catal.

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We report the development of highly enantio- and regioselective Pd-catalyzed intermolecular hydroaminations of challenging 1,4-disubstituted acyclic dienes. Several aryl/alkyl-disubstituted dienes and a sterically differentiated alkyl/alkyl-disubstituted diene undergo coupling with a variety of secondary aliphatic amines, indoline, and primary anilines to generate allylic amines with myriad α-alkyl groups in up to 78% yield, >98:2 rr, and 98.5:1.5 er. A number of experiments, including deuterium labeling and transamination studies, shed light on mechanistic details of the reaction, such as the reversibility of individual steps of the proposed catalytic cycle and of the reaction as a whole.

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Section: Resultsmentioning

confidence: 99%

Development and Mechanistic Investigations of Enantioselective Pd-Catalyzed Intermolecular Hydroaminations of Internal Dienes

Park

Malcolmson

2018

ACS Catal.

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“…[11] Based on the above mechanistic studies and literature reports, [8,9] the following plausible mechanism is proposed for this novel alkyl-Heck reaction of diazo compounds and Ntosylhydrazones (Scheme 5). Path a begins with an oxidative addition of HX with Pd 0 to generate active HPdXL 2 species, [18] which via a denitrogenative reaction with diazo compound produces Pd-carbene intermediate A. A subse- [a] 0.1 mmol scale; 4 a:2 a = 1:1.1.…”

Section: Methodsmentioning

confidence: 99%

Visible Light Induced Brønsted Acid Assisted Pd‐Catalyzed Alkyl Heck Reaction of Diazo Compounds and N‐Tosylhydrazones

et al. 2021

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A mild visible light-induced palladium-catalyzed alkyl Heck reaction of diazo compounds and N-tosylhydrazones is reported. A broad range of vinyl arenes and heteroarenes with high functional group tolerance, as well as a range of different diazo compounds, can efficiently undergo this transformation. This method features Brønsted acidassisted generation of hybrid palladium C(sp 3 )-centered radical intermediate, which allowed for new selective C À H functionalization protocol.Scheme 1. The reactivity of diazo compounds with alkenes.

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“…31 Considering this sequence in reverse, we envisioned that base•HX species could be used as practical HX surrogates to controllably generate the desired H− Pd(II)−X species in situ. 32 This would then promote the desired enyne hydrohalogenation via the transfer of both the hydride and halide ligands to the substrate.…”

Section: ■ Introductionmentioning

confidence: 99%

Palladium-Catalyzed Hydrohalogenation of 1,6-Enynes: Hydrogen Halide Salts and Alkyl Halides as Convenient HX Surrogates

Petrone

Franzoni

et al. 2017

J. Am. Chem. Soc.

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Difficulties associated with handling H and CO in metal-catalyzed processes have led to the development of chemical surrogates to these species. Despite many successful examples using this strategy, the application of convenient hydrogen halide (HX) surrogates in catalysis has lagged behind considerably. We now report the use of ammonium halides as HX surrogates to accomplish a Pd-catalyzed hydrohalogenation of enynes. These safe and practical salts avoid many drawbacks associated with traditional HX sources including toxicity and corrosiveness. Experimental and computational studies support a reaction mechanism involving a crucial E-to-Z vinyl-Pd isomerization and a carbon-halogen bond-forming reductive elimination. Furthermore, rare examples of C(sp)-Br and -Cl reductive elimination from Pd(II) as well as transfer hydroiodination using 1-iodobutane as an alternate HI surrogate are also presented.

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Palladium-catalyzed additions of amines to conjugated dienes. Alteration of behavior of triphenylphosphine-palladium catalysts with amine hydroiodide salts

Cited by 46 publications

References 0 publications

Development and Mechanistic Investigations of Enantioselective Pd-Catalyzed Intermolecular Hydroaminations of Internal Dienes

Development and Mechanistic Investigations of Enantioselective Pd-Catalyzed Intermolecular Hydroaminations of Internal Dienes

Visible Light Induced Brønsted Acid Assisted Pd‐Catalyzed Alkyl Heck Reaction of Diazo Compounds and N‐Tosylhydrazones

Palladium-Catalyzed Hydrohalogenation of 1,6-Enynes: Hydrogen Halide Salts and Alkyl Halides as Convenient HX Surrogates

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