Palladium Theory of Aqueous-Phase Heck Alkynylations for Intensification of Discovery and Manufacture

Jasmine C. Sabio, Ria C. Domier, Jane N. Moore, Kevin H. Shaughnessy, Ryan Hartman

Research output: Contribution to journalArticle

Abstract

The influence of water on the catalysis of biphasic Heck alkynylation, a family of palladium-catalyzed carbon-carbon bond formations, was investigated. Kinetic theory derived from Hatta moduli and pseudo-stationary-state approximations discovered that water, in coordination, reductive elimination, and product dissociation reaction steps of the deprotonation catalytic cycle, increases Gibbs energy barriers compared to values previously estimated by density functional theory calculations of purely organic syntheses involving an aryl iodide. On the contrary, water reduces the energy barrier of reductive elimination in the carbopalladation catalytic cycle. Quantum tunneling in proton transfer mechanism might account for the change. The discoveries permitted E-factor predictions that could someday help reduce chemical wastes generated during materials, natural products, and pharmaceutical manufactures. Theoretical groundwork is laid that enables data-driven research in the academic laboratory and data-driven development by the process chemist.

Original languageEnglish (US)
Pages (from-to)1717-1725
Number of pages9
JournalChemical Engineering and Technology
Volume38
Issue number10
DOIs
StatePublished - Oct 1 2015

Fingerprint

Palladium
Energy barriers
Water
Carbon
Chemical wastes
Deprotonation
Proton transfer
Kinetic theory
Iodides
Gibbs free energy
Biological Products
Drug products
Catalysis
Density functional theory
Pharmaceutical Preparations

Keywords

  • Data-driven chemistry
  • E-factor
  • Gibbs free energy
  • Heck alkynylation
  • Process intensification

ASJC Scopus subject areas

  • Chemical Engineering(all)
  • Chemistry(all)
  • Industrial and Manufacturing Engineering

Cite this

Palladium Theory of Aqueous-Phase Heck Alkynylations for Intensification of Discovery and Manufacture. / Sabio, Jasmine C.; Domier, Ria C.; Moore, Jane N.; Shaughnessy, Kevin H.; Hartman, Ryan.

In: Chemical Engineering and Technology, Vol. 38, No. 10, 01.10.2015, p. 1717-1725.

Research output: Contribution to journalArticle

Sabio, Jasmine C. ; Domier, Ria C. ; Moore, Jane N. ; Shaughnessy, Kevin H. ; Hartman, Ryan. / Palladium Theory of Aqueous-Phase Heck Alkynylations for Intensification of Discovery and Manufacture. In: Chemical Engineering and Technology. 2015 ; Vol. 38, No. 10. pp. 1717-1725.
@article{313156443db94d12b76d7b99474a89f4,
title = "Palladium Theory of Aqueous-Phase Heck Alkynylations for Intensification of Discovery and Manufacture",
abstract = "The influence of water on the catalysis of biphasic Heck alkynylation, a family of palladium-catalyzed carbon-carbon bond formations, was investigated. Kinetic theory derived from Hatta moduli and pseudo-stationary-state approximations discovered that water, in coordination, reductive elimination, and product dissociation reaction steps of the deprotonation catalytic cycle, increases Gibbs energy barriers compared to values previously estimated by density functional theory calculations of purely organic syntheses involving an aryl iodide. On the contrary, water reduces the energy barrier of reductive elimination in the carbopalladation catalytic cycle. Quantum tunneling in proton transfer mechanism might account for the change. The discoveries permitted E-factor predictions that could someday help reduce chemical wastes generated during materials, natural products, and pharmaceutical manufactures. Theoretical groundwork is laid that enables data-driven research in the academic laboratory and data-driven development by the process chemist.",
keywords = "Data-driven chemistry, E-factor, Gibbs free energy, Heck alkynylation, Process intensification",
author = "Sabio, {Jasmine C.} and Domier, {Ria C.} and Moore, {Jane N.} and Shaughnessy, {Kevin H.} and Ryan Hartman",
year = "2015",
month = "10",
day = "1",
doi = "10.1002/ceat.201500117",
language = "English (US)",
volume = "38",
pages = "1717--1725",
journal = "Chemical Engineering and Technology",
issn = "0930-7516",
publisher = "Wiley-VCH Verlag",
number = "10",

}

TY - JOUR

T1 - Palladium Theory of Aqueous-Phase Heck Alkynylations for Intensification of Discovery and Manufacture

AU - Sabio, Jasmine C.

AU - Domier, Ria C.

AU - Moore, Jane N.

AU - Shaughnessy, Kevin H.

AU - Hartman, Ryan

PY - 2015/10/1

Y1 - 2015/10/1

N2 - The influence of water on the catalysis of biphasic Heck alkynylation, a family of palladium-catalyzed carbon-carbon bond formations, was investigated. Kinetic theory derived from Hatta moduli and pseudo-stationary-state approximations discovered that water, in coordination, reductive elimination, and product dissociation reaction steps of the deprotonation catalytic cycle, increases Gibbs energy barriers compared to values previously estimated by density functional theory calculations of purely organic syntheses involving an aryl iodide. On the contrary, water reduces the energy barrier of reductive elimination in the carbopalladation catalytic cycle. Quantum tunneling in proton transfer mechanism might account for the change. The discoveries permitted E-factor predictions that could someday help reduce chemical wastes generated during materials, natural products, and pharmaceutical manufactures. Theoretical groundwork is laid that enables data-driven research in the academic laboratory and data-driven development by the process chemist.

AB - The influence of water on the catalysis of biphasic Heck alkynylation, a family of palladium-catalyzed carbon-carbon bond formations, was investigated. Kinetic theory derived from Hatta moduli and pseudo-stationary-state approximations discovered that water, in coordination, reductive elimination, and product dissociation reaction steps of the deprotonation catalytic cycle, increases Gibbs energy barriers compared to values previously estimated by density functional theory calculations of purely organic syntheses involving an aryl iodide. On the contrary, water reduces the energy barrier of reductive elimination in the carbopalladation catalytic cycle. Quantum tunneling in proton transfer mechanism might account for the change. The discoveries permitted E-factor predictions that could someday help reduce chemical wastes generated during materials, natural products, and pharmaceutical manufactures. Theoretical groundwork is laid that enables data-driven research in the academic laboratory and data-driven development by the process chemist.

KW - Data-driven chemistry

KW - E-factor

KW - Gibbs free energy

KW - Heck alkynylation

KW - Process intensification

UR - http://www.scopus.com/inward/record.url?scp=84942835140&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84942835140&partnerID=8YFLogxK

U2 - 10.1002/ceat.201500117

DO - 10.1002/ceat.201500117

M3 - Article

AN - SCOPUS:84942835140

VL - 38

SP - 1717

EP - 1725

JO - Chemical Engineering and Technology

JF - Chemical Engineering and Technology

SN - 0930-7516

IS - 10

ER -