Identification of vicinal diols using a diagnostic ion derived from the electron ionization of orthoester functional groups

Design of materials with novel sensitivities and smart behaviour is important for the development of smart systems with automated responsiveness. We have recently reported the synthesis of hydrogels, cross-linked by N,N'-diallyltartardiamide (DAT). The covalent DAT-crosslinking points have vicinal diols which can be easily cleaved with periodate, generating valuable a-oxo-aldehyde functional groups, useful for further chemical modification. Based on those findings, we envisioned that a self-healable hydrogel could be obtained by incorporation of primary amino functional groups, from <a>2-aminoethyl methacrylate </a>hydrochloride (AEMA), coexisting with DAT into the same network. The a-oxo-aldehyde groups generated after the reaction with periodate would arise in the immediate environment of amine groups to form imine cross-links. For this purpose, DAT-crosslinked hydrogels were synthesized and carefully characterized. The cleavage of DAT-crosslinks with periodate promoted changes in the mechanical and swelling properties of the materials. As expected, a self-healing behavior was observed, based on the spontaneous formation of imine covalent bonds. In addition, we surprisingly found a combination of fast vicinal diols cleavage and a low speed self-crosslinking reaction by imine formation. Consequently, it was found a time-window in which a periodate-treated polymer was obtained in a transient liquid state, which can be exploited to choose the final shape of the material, before automated gelling. The singular properties attained on these hydrogels could be useful for developing sensors, actuators, among other smart systems.

Oxidative cyclization for the synthesis of complex tetrahydrofuran-containing natural products

Pure and Applied Chemistry ◽

10.1351/pac-con-12-10-25 ◽

2013 ◽

Vol 85 (6) ◽

pp. 1175-1184 ◽

Cited By ~ 4

Author(s):

Robert D. C. Pullin ◽

Radosław M. Lipiński ◽

Timothy J. Donohoe

Keyword(s):

Natural Products ◽

Amino Acid ◽

Functional Groups ◽

Lewis Acid ◽

Excitatory Amino Acid ◽

Oxidative Cyclization ◽

Annonaceous Acetogenins ◽

Hydride Shift ◽

Vicinal Diols ◽

Shift Sequence

The osmium-catalyzed oxidative cyclization of vicinal diols onto proximal olefins to generate 2,5-cis-substituted tetrahydrofurans (THFs) has been exploited as the key step for the construction of several complex THF-containing natural products, namely, the annonaceous acetogenins cis-sylvaticin, sylvaticin, and the excitatory amino acid neo-dysiherbaine A. Recently modified conditions that employ a Lewis acid enable the cyclization to proceed under milder conditions, providing greater tolerance to acid-sensitive functional groups, as demonstrated in two of the syntheses. Flexibility for the construction of 2,5-trans-THFs was demonstrated in the synthesis of sylvaticin by utilization of an intramolecular hydride-shift sequence.

Imine Based Self-Healing Hydrogel Triggered by Periodate

10.26434/chemrxiv.12592322.v1 ◽

2020 ◽

Author(s):

Alexis Wolfel ◽

Cecilia Inés Alvarez Igarzabal ◽

Marcelo Ricardo Romero

Keyword(s):

Functional Groups ◽

Time Window ◽

Crosslinking Reaction ◽

Self Healing ◽

Swelling Properties ◽

Covalent Bonds ◽

Smart Systems ◽

Primary Amino ◽

Vicinal Diols ◽

Aldehyde Groups

Design of materials with novel sensitivities and smart behaviour is important for the development of smart systems with automated responsiveness. We have recently reported the synthesis of hydrogels, cross-linked by N,N'-diallyltartardiamide (DAT). The covalent DAT-crosslinking points have vicinal diols which can be easily cleaved with periodate, generating valuable a-oxo-aldehyde functional groups, useful for further chemical modification. Based on those findings, we envisioned that a self-healable hydrogel could be obtained by incorporation of primary amino functional groups, from <a>2-aminoethyl methacrylate </a>hydrochloride (AEMA), coexisting with DAT into the same network. The a-oxo-aldehyde groups generated after the reaction with periodate would arise in the immediate environment of amine groups to form imine cross-links. For this purpose, DAT-crosslinked hydrogels were synthesized and carefully characterized. The cleavage of DAT-crosslinks with periodate promoted changes in the mechanical and swelling properties of the materials. As expected, a self-healing behavior was observed, based on the spontaneous formation of imine covalent bonds. In addition, we surprisingly found a combination of fast vicinal diols cleavage and a low speed self-crosslinking reaction by imine formation. Consequently, it was found a time-window in which a periodate-treated polymer was obtained in a transient liquid state, which can be exploited to choose the final shape of the material, before automated gelling. The singular properties attained on these hydrogels could be useful for developing sensors, actuators, among other smart systems.

Interaction of remote functional groups (amide and amine) in steroidal compounds after electron ionization

Organic Mass Spectrometry ◽

10.1002/oms.1210251008 ◽

1990 ◽

Vol 25 (10) ◽

pp. 527-536 ◽

Cited By ~ 7

Author(s):

Pierre Longevialle ◽

Guy Bouchoux ◽

Yannik Hoppilliard

Keyword(s):

Functional Groups ◽

Electron Ionization