Commodity Polymers to Functional Aminated Materials: Single-Step and Atom-Economic Synthesis by Hydroaminoalkylation

Scott, Sabrina S.; Roşca, Sorin-Claudiu; Gilmour, Damon J.; Brant, Patrick; Schafer, Laurel L.

doi:10.1021/acsmacrolett.1c00519

Cited by 5 publications

(10 citation statements)

References 52 publications

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“…91 Our work on tantalum-catalyzed hydroaminoalkylation of vinyl terminated polypropylene (VTPP) demonstrated that hydroaminoalkylation is a viable postpolymerisation amination method and regioselective formation of the branched products was observed. 61 Such postpolymerization modifications can be challenging to catalyze due to the limited solubility and viscosity of the polymer, but the reactivity of the Ti(NMe 2 ) 4 / L1 system with challenging and diverse alkene substrates 31 ( vide supra ) suggests that this system could also be used with challenging macromolecular substrates for postpolymerisation (Table 1) and would offer a “green” advance.…”

Section: Resultsmentioning

confidence: 99%

“…This trend is also observed with the tantalum catalyzed hydroaminoalkylation which required 20 mol% tantalum catalyst for VTPPs with M n = 8500 g mol −1 . 61…”

Section: Resultsmentioning

confidence: 99%

“…This trend is also observed with the tantalum catalyzed hydroaminoalkylation which required 20 mol% tantalum catalyst for VTPPs with M n = 8500 g mol −1 . 61 Up to 83% (entry 7) isolated yields were obtained for this series of materials. Materials derived from VT230 and VT350 could be purified by filtering through a short silica pad and removing solvents in vacuo.…”

Section: Functionalized Polymersmentioning

confidence: 94%

“…This work also reports the first example of using a titanium catalyst for challenging postpolymerisation hydroaminoalkylation of vinyl terminated polypropylene (VTPP) to produce branched amine-terminated functionalized oligomers (Scheme 1b). 61,62 Unlike small molecule hydroaminomethylation to access branched products, there are no examples of post-polymerization hydroaminomethylation. Such materials are potentially industrially relevant, as they can potentially be used as surface modifiers [63][64][65][66][67] and responsive materials.…”

Section: Introductionmentioning

confidence: 99%

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Accessing secondary amine containing fine chemicals and polymers with an earth-abundant hydroaminoalkylation catalyst

et al. 2023

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Section: Resultsmentioning

confidence: 99%

“…This trend is also observed with the tantalum catalyzed hydroaminoalkylation which required 20 mol% tantalum catalyst for VTPPs with M n = 8500 g mol −1 . 61…”

Section: Resultsmentioning

confidence: 99%

Section: Functionalized Polymersmentioning

confidence: 94%

Section: Introductionmentioning

confidence: 99%

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Accessing secondary amine containing fine chemicals and polymers with an earth-abundant hydroaminoalkylation catalyst

et al. 2023

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“…The high reactivity observed with the cyclic ureate catalyst has made this system suitable for postpolymerization modification for functional materials synthesis (Scheme 27). 110 Using Ta-catalyzed hydroaminoalkylation, vinyl-terminated polypropylene can be directly and quantitatively converted to amine-terminated polypropylene. Early transi- tion-metal, atom-economic hydroaminoalkylation is ideally suited for postpolymerization modification, as there are no byproducts and no deprotection protocols required.…”

Section: Early Transition-metalmentioning

confidence: 99%

Hydroaminoalkylation for the Catalytic Addition of Amines to Alkenes or Alkynes: Diverse Mechanisms Enable Diverse Substrate Scope

2022

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Hydroaminoalkylation is a powerful, atom-economic catalytic reaction for the reaction of amines with alkenes and alkynes. This C–H functionalization reaction allows for the atom-economic alkylation of amines using simple alkenes or alkynes as the alkylating agents. This transformation has significant potential for transformative approaches in the pharmaceutical, agrochemical, and fine chemical industries in the preparation of selectively substituted amines and N-heterocycles and shows promise in materials science for the synthesis of functional and responsive aminated materials. Different early transition-metal, late transition-metal, and photoredox catalysts mediate hydroaminoalkylation by distinct mechanistic pathways. These mechanistic insights have resulted in the development of new catalysts and reaction conditions to realize hydroaminoalkylation with a broad range of substrates: activated and unactivated, terminal and internal, C–C double and triple bonds with aryl or alkyl primary, secondary, or tertiary amines, including N-heterocyclic amines. By deploying select catalysts with specific substrate combinations, control over regioselectivity, diastereoselectivity, and enantioselectivity has been realized. Key barriers to widespread adoption of this reaction include air and moisture sensitivity for early transition-metal catalysts as well as a heavy dependence on amine protecting or directing groups for late transition-metal or photocatalytic routes. Advances in improved catalyst robustness, substrate scope, and regio-/stereoselective reactions with early- and late transition-metal catalysts, as well as photoredox catalysis, are highlighted, and opportunities for further catalyst and reaction development are included. This perspective shows that hydroaminoalkylation has the potential to be a disruptive and transformative strategy for the synthesis of selectively substituted amines and N-heterocycles from simple amines and alkenes.

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Amine-Functionalized Polybutadiene Synthesis by Tunable Postpolymerization Hydroaminoalkylation

Scott,

Kaur,

Zheng

et al. 2023

J. Am. Chem. Soc.

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Early transition metal-catalyzed hydroaminoalkylation is a powerful single-step method to selectively add amines to polybutadienes, offering an efficient strategy to access amine-functionalized polyolefins. Aryl and alkyl secondary amines were used with a tantalum catalyst to functionalize both 28 wt% (PBD13) and 70 wt% (PBD50) 1,2-polybutadiene polymers. The degree of amination was controlled by modifying amine and catalyst loading in both small- and multigram-scale reactions. The vinyl groups of 1,2-polybutadiene were aminated with ease, and unexpectedly the hydroaminoalkylation of challenging internal alkenes of the 1,4-polybutadiene unit was observed. This unanticipated reactivity was proposed to be due to a directing group effect. This hypothesis was supported with small-molecule model substrates, which also showed directed internal alkene amination. Increasing degrees of amination resulted in materials with dramatically higher and tunable glass transition temperature (T g) values, due to the dynamic cross-linking accessible to hydrogen-bonding, amine-containing materials. Primary amine-functionalized polybutadiene was also prepared, demonstrating that a broad new class of amine-containing polyolefins can be accessed by postpolymerization hydroaminoalkylation.

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Commodity Polymers to Functional Aminated Materials: Single-Step and Atom-Economic Synthesis by Hydroaminoalkylation

Cited by 5 publications

References 52 publications

Accessing secondary amine containing fine chemicals and polymers with an earth-abundant hydroaminoalkylation catalyst

Accessing secondary amine containing fine chemicals and polymers with an earth-abundant hydroaminoalkylation catalyst

Hydroaminoalkylation for the Catalytic Addition of Amines to Alkenes or Alkynes: Diverse Mechanisms Enable Diverse Substrate Scope

Amine-Functionalized Polybutadiene Synthesis by Tunable Postpolymerization Hydroaminoalkylation

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