Kinetic Modeling Enables Understanding of Off-Cycle Processes in Pd-Catalyzed Amination of Five-Membered Heteroaryl Halides DOI
Elaine C. Reichert, Jakob C. Dahl, Klavs F. Jensen

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 20, 2024

The mechanism of Pd-catalyzed amination five-membered heteroaryl halides was investigated by integrating experimental kinetic analysis with modeling through predictive testing and likelihood ratio analysis, revealing an atypical productive coupling pathway multiple off-cycle events. GPhos-supported Pd catalyst, along the moderate-strength base NaOTMS, previously found to promote efficient between secondary amines. However, slight deviations from optimal concentration, temperature, and/or solvent resulted in significantly lower yields, contrary typical reaction optimization trends. We that 4-bromothiazole piperidine proceeds uncommon which NaOTMS base, rather than amine, binds first oxidative addition complex; resulting OTMS-bound species is resting state. Formation Pd-amido complex via base/amine exchange identified as turnover-limiting step, unlike other reported catalyst systems for reductive elimination turnover-limiting. determined amine-bound complex, usually on-cycle intermediate, instead a reversibly generated species, base-mediated decomposition primary irreversible deactivation pathway. Predictive were key identification these processes, providing insight into minor mechanistic pathways are difficult observe experimentally. Collectively, this report reveals unique enabling features Pd-GPhos/NaOTMS system, implementing insights improve yields particularly challenging reactions. Moreover, findings highlight utility applying tests models rapid evaluation possibilities small-molecule catalytic systems.

Язык: Английский

Paving the road towards automated homogeneous catalyst design DOI Creative Commons
Adarsh V. Kalikadien,

A.H. Mirza,

Aydin Najl Hossaini

и другие.

ChemPlusChem, Год журнала: 2024, Номер 89(7)

Опубликована: Янв. 26, 2024

In the past decade, computational tools have become integral to catalyst design. They continue offer significant support experimental organic synthesis and catalysis researchers aiming for optimal reaction outcomes. More recently, data-driven approaches utilizing machine learning garnered considerable attention their expansive capabilities. This Perspective provides an overview of diverse initiatives in realm design introduces our automated tailored high-throughput silico exploration chemical space. While valuable insights are gained through methods analysis space, degree automation modularity key. We argue that integration data-driven, modular workflows is key enhancing homogeneous on unprecedented scale, contributing advancement research.

Язык: Английский

Процитировано

15
A rapid-heating copper block reactor system for improved isothermal kinetics of polyethylene pyrolysis DOI
Abdulrahman Alzailaie, Ibraheam Al‐Shankiti,

Mohammed Babkoor

и другие.

Chemical Engineering Journal, Год журнала: 2025, Номер unknown, С. 163298 - 163298

Опубликована: Май 1, 2025

Язык: Английский

Процитировано

0
Active learning enabled reactor characterization for mass transfer in aerobic oxidation reactions DOI Creative Commons
Ajit Vikram, Keith Mattern, Shane T. Grosser

и другие.

Reaction Chemistry & Engineering, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 18, 2024

A generalizable active learning framework enables accurate prediction of mass transfer coefficients ( k L a ), and iterative design experiments to efficiently characterize new reactor configurations with minimal experimental trials.

Язык: Английский

Процитировано

0
Kinetic Modeling Enables Understanding of Off-Cycle Processes in Pd-Catalyzed Amination of Five-Membered Heteroaryl Halides DOI
Elaine C. Reichert, Jakob C. Dahl, Klavs F. Jensen

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 20, 2024

The mechanism of Pd-catalyzed amination five-membered heteroaryl halides was investigated by integrating experimental kinetic analysis with modeling through predictive testing and likelihood ratio analysis, revealing an atypical productive coupling pathway multiple off-cycle events. GPhos-supported Pd catalyst, along the moderate-strength base NaOTMS, previously found to promote efficient between secondary amines. However, slight deviations from optimal concentration, temperature, and/or solvent resulted in significantly lower yields, contrary typical reaction optimization trends. We that 4-bromothiazole piperidine proceeds uncommon which NaOTMS base, rather than amine, binds first oxidative addition complex; resulting OTMS-bound species is resting state. Formation Pd-amido complex via base/amine exchange identified as turnover-limiting step, unlike other reported catalyst systems for reductive elimination turnover-limiting. determined amine-bound complex, usually on-cycle intermediate, instead a reversibly generated species, base-mediated decomposition primary irreversible deactivation pathway. Predictive were key identification these processes, providing insight into minor mechanistic pathways are difficult observe experimentally. Collectively, this report reveals unique enabling features Pd-GPhos/NaOTMS system, implementing insights improve yields particularly challenging reactions. Moreover, findings highlight utility applying tests models rapid evaluation possibilities small-molecule catalytic systems.

Язык: Английский

Процитировано

0