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Title: Inter- and Intramolecular Cooperativity Effects in Alkanolamine-Based Acid–Base Heterogeneous Organocatalysts

Journal Article · · ACS Omega
 [1];  [1]; ORCiD logo [1]
  1. School of Chemical &, Biomolecular Engineering, Georgia Institute of Technology, 311 Ferst Dr., Atlanta, Georgia 30332-0100, United States
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Intramolecular cooperativity in heterogeneous organocatalysts is investigated using alkanolamine-functionalized silica acid–base catalysts for the aldol condensation reaction of 4-nitrobenzaldehyde and acetone. Two series of catalysts, one with and one without silanol-capping, are synthesized with varied alkyl linker lengths (two to five) connecting secondary amine and terminal hydroxyl functionalities. The reactivity of these catalysts is assessed to determine the relative potential for intermolecular (silane amine–surface silanol) vs intramolecular (amine–hydroxyl within a single silane) cooperativity, the impact of inhibitory surface–silane interactions, and the role of alkyl linker length and flexibility. For the array of catalysts tested, those with longer linker lengths generally give increased catalytic activity, although the turnover frequency trends differ between catalysts with and without surface silanol capping. Catalysts with alkyl-substituted amines lacking a terminal hydroxyl demonstrate an adverse effect of chain length, where the larger alkyl substituent on the amine provides steric hindrance depressing catalytic activity, while giving additional evidence for improved rates afforded by intramolecular cooperativity in the alkanolamine materials. The silanol-capped alkanolamine catalyst with the longest alkyl linker is found to be the most active alkanolamine catalyst due to its hydrophobized surface, which removes hypothesized silanol–alkanolamine inhibitory interactions, with the sufficient length and flexibility of its amine–hydroxyl linker allowing for favorable conformations for cooperativity. This study demonstrates the feasibility of and important factors affecting intramolecular cooperative activity in acid–base heterogeneous organocatalysis.

Research Organization:
Georgia Institute of Technology, Atlanta, GA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
FG02-03ER15459
OSTI ID:
1490772
Alternate ID(s):
OSTI ID: 1508824; OSTI ID: 1657460
Journal Information:
ACS Omega, Journal Name: ACS Omega Vol. 4 Journal Issue: 1; ISSN 2470-1343
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 6 works
Citation information provided by
Web of Science

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Figures / Tables (9)

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ldol condensation
Catalysis
Catalysts
Mechanical properties
Organic compounds and Functional groups
Reaction kinetics
Reaction mechanism
Surface treatment