Regio- and Stereoselective Synthesis of Bicyclic Limonene-Based Chiral Aminodiols and Spirooxazolidines

Research output: Contribution to journalArticle

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Abstract

A library of monoterpene-based aminodiols was synthesized and applied as chiral catalysts in the addition of diethylzinc to benzaldehyde. The reduction of a bicyclic α-methylene ketone, derived from natural (−)-limonene followed by epoxidation, gave the key epoxy alcohol intermediate. Ring opening of the oxirane ring with primary amines induced by lithium perchlorate afforded the required aminodiols. Substituent-dependent ring closure of the secondary aminodiols with formaldehyde resulted in both spirooxazolidines and a fused 1,3-oxazine. Cyclization reactions of the studied aminodiols, resulting in spirocyclic oxazolidines and an isomeric perhydro-1,3-oxazine-fused compound along with the possible iminium intermediates, were analyzed by a systematic series of comparative DFT models performed at the B3LYP/6-31+G(d,p) level of theory.

Original languageEnglish
Pages (from-to)13607-13615
Number of pages9
JournalChemistry - A European Journal
Volume24
Issue number51
DOIs
Publication statusPublished - Sep 12 2018

Fingerprint

Oxazines
Monoterpenes
Epoxidation
Cyclization
Ketones
Formaldehyde
Discrete Fourier transforms
Amines
Lithium
Alcohols
Ethylene Oxide
Catalysts
limonene

Keywords

  • aminodiols
  • asymmetric synthesis
  • molecular modeling
  • oxazolidines
  • terpenoids

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Regio- and Stereoselective Synthesis of Bicyclic Limonene-Based Chiral Aminodiols and Spirooxazolidines. / Le, Tam Minh; Csámpai, A.; Fülöp, F.; Szakonyi, Z.

In: Chemistry - A European Journal, Vol. 24, No. 51, 12.09.2018, p. 13607-13615.

Research output: Contribution to journalArticle

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AU - Le, Tam Minh

AU - Csámpai, A.

AU - Fülöp, F.

AU - Szakonyi, Z.

PY - 2018/9/12

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N2 - A library of monoterpene-based aminodiols was synthesized and applied as chiral catalysts in the addition of diethylzinc to benzaldehyde. The reduction of a bicyclic α-methylene ketone, derived from natural (−)-limonene followed by epoxidation, gave the key epoxy alcohol intermediate. Ring opening of the oxirane ring with primary amines induced by lithium perchlorate afforded the required aminodiols. Substituent-dependent ring closure of the secondary aminodiols with formaldehyde resulted in both spirooxazolidines and a fused 1,3-oxazine. Cyclization reactions of the studied aminodiols, resulting in spirocyclic oxazolidines and an isomeric perhydro-1,3-oxazine-fused compound along with the possible iminium intermediates, were analyzed by a systematic series of comparative DFT models performed at the B3LYP/6-31+G(d,p) level of theory.

AB - A library of monoterpene-based aminodiols was synthesized and applied as chiral catalysts in the addition of diethylzinc to benzaldehyde. The reduction of a bicyclic α-methylene ketone, derived from natural (−)-limonene followed by epoxidation, gave the key epoxy alcohol intermediate. Ring opening of the oxirane ring with primary amines induced by lithium perchlorate afforded the required aminodiols. Substituent-dependent ring closure of the secondary aminodiols with formaldehyde resulted in both spirooxazolidines and a fused 1,3-oxazine. Cyclization reactions of the studied aminodiols, resulting in spirocyclic oxazolidines and an isomeric perhydro-1,3-oxazine-fused compound along with the possible iminium intermediates, were analyzed by a systematic series of comparative DFT models performed at the B3LYP/6-31+G(d,p) level of theory.

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KW - asymmetric synthesis

KW - molecular modeling

KW - oxazolidines

KW - terpenoids

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