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PreprintCC BYChemRxiv

Unusual reactivities of “NONO” calix[4]arene aluminum complexes

  • Matteo Cardoso1
  • Frank Schaper1
  1. 1Centre in Green Chemistry and Catalysis, Department of Chemistry, University of Montreal, 2900 Edouard Montpetit Blvd, Montreal, Quebec, H3T 1J4
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Abstract

Reaction of dibenzylaminocalix[4]arene, L1H2, with aluminum alkyls did not lead to deprotonation of both phenolic groups but provided aluminum or aluminate complexes containing phenolic OH or anilinium NH2 + groups in the presence of aluminum alkyl groups. Upon heating aluminum complexes L1AlMe and L1AlCl were obtained. Reaction of L1AlMe with amines led to amido complexes, either of the ancillary amine or the aniline moiety of L1. Further reaction with isopropanol yielded L1AlOiPr. Heating in the absence of amine afforded the phenyl complex L1AlC6D5 by activation of the NMR solvent. Reaction with two equivalents of AlMe3 led to -H abstraction from methyl to form methylene-bridged (L1-2H)(AlMe)2CH2. Reactions of bis(S,S-2-(dimethylamino)cyclohexyl)amino) calix[4]arene, L2H2, with AlEt2Cl or AlMe3 led directly to the anilido complex (L2-H)Al. Reaction with two equivalents of AlMe3 yielded (L2-2H)Al2CH2 after -H abstraction from methyl. Both compounds reacted with isopropanol to form L2AlOiPr. Isopropoxide complexes L1AlOiPr and L2AlOiPr were moderately active in lactide polymerization (yielding essentially atactic polylactide) and the Meerwein-Ponndorf-Verley reduction of benzophenone. Reaction of methylene-bridged (L2-2H)Al2CH2 with benzophenone afforded diphenylethylene in transition-metal-free methylenation.

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Cite

BibTeXRIS
BibTeX
@misc{cardoso2026unusual,
  title = {{Unusual reactivities of “NONO” calix[4]arene aluminum complexes}},
  author = {Matteo Cardoso and Frank Schaper},
  howpublished = {ChemRxiv},
  year = {2026},
  month = sep,
  doi = {10.26434/chemrxiv.15008690/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008690/v1},
  note = {CC BY},
}
RIS
TY  - UNPB
TI  - Unusual reactivities of “NONO” calix[4]arene aluminum complexes
AU  - Matteo Cardoso
AU  - Frank Schaper
PY  - 2026
DA  - 2026/09/11
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15008690/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008690/v1
AB  - Reaction of dibenzylaminocalix[4]arene, L1H2, with aluminum alkyls did not lead to deprotonation of both phenolic groups but provided aluminum or aluminate complexes containing phenolic OH or anilinium NH2 + groups in the presence of aluminum alkyl groups. Upon heating aluminum complexes L1AlMe and L1AlCl were obtained. Reaction of L1AlMe with amines led to amido complexes, either of the ancillary amine or the aniline moiety of L1. Further reaction with isopropanol yielded L1AlOiPr. Heating in the absence of amine afforded the phenyl complex L1AlC6D5 by activation of the NMR solvent. Reaction with two equivalents of AlMe3 led to -H abstraction from methyl to form methylene-bridged (L1-2H)(AlMe)2CH2. Reactions of bis(S,S-2-(dimethylamino)cyclohexyl)amino) calix[4]arene, L2H2, with AlEt2Cl or AlMe3 led directly to the anilido complex (L2-H)Al. Reaction with two equivalents of AlMe3 yielded (L2-2H)Al2CH2 after -H abstraction from methyl. Both compounds reacted with isopropanol to form L2AlOiPr. Isopropoxide complexes L1AlOiPr and L2AlOiPr were moderately active in lactide polymerization (yielding essentially atactic polylactide) and the Meerwein-Ponndorf-Verley reduction of benzophenone. Reaction of methylene-bridged (L2-2H)Al2CH2 with benzophenone afforded diphenylethylene in transition-metal-free methylenation.
ER  -