Synthesis of Some Selectively N-Protected (1S,2S)-p-Nitrophenylserinol–Based Diamino-1,3-dioxanes and Tripodands

Abstract

The unconventional methodology for the non-epimerizable cycloacetalization of optically active (1S,2S)-2-amino-1-(4-nitrophenyl)propane-1,3-diol (p-nitrophenylserinol) (condensed H₂SO₄ 96% as solvent and catalyst, i.e., sulfuric transacetalization) producing (2R,4S,5S) diamino-1,3-dioxanes was enlarged by the use of N-protected forms of 2,2-dimethoxyethylamine (DMEA, aminoacetaldehyde dimethylacetal). Conversely, N-protected derivatives of p-nitrophenylserinol were successfully cyclocondensed with DMEA in the same sulfuric conditions. N-Functionalization of DMEA upon treatment with trimesic acid trichloride and cyanuric chloride yielded the corresponding triple amide and melamine, respectively. Their adapted sulfuric transacetalization in triplicate in reaction with arylserinols (aryl: phenyl, p-nitrophenyl) afforded a new series of optically active tripodands.

GRAPHICAL ABSTRACT

Keywords:

• Protecting groups
• serinols
• transacetalization
• tripodands

Supporting Information

(Typical) procedures for preparations of compounds 1a, 1b, 1c, 3b, 4b, 4c, 1d, and 1e; full analytical data of compounds 1a, 1b, 1c, 2b, 3b, 4b, 4c, 2a, 5a, 5b, 1d, 1e, 6e, and 7d; ¹H and ¹³C NMR spectra of compounds 1a, 1b, 1c, 2b, 4b, 4c, 3b, 2a, 5a, 5b, 1d, 1e, 6d, 6e, and 7d; and MS of compounds 6d, 6e, and 7d for this article can be accessed on the publisher’s website.