Stereoselective synthesis of pinane-type tridentate aminodiols and their application in the enantioselective addition of diethylzinc to benzaldehyde

Kinga Csillag, Lukács Németh, T. Martinek, Z. Szakonyi, F. Fülöp

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Abstract

A library of pinane-based aminodiols were prepared from commercially available (1R)-(-)-myrtenol (-)-1. Compound (-)-1 was transformed into allyl trichloroacetamide (+)-2 via the acetimidate, followed by the Overman rearrangement. In order obtain the aminodiol structure, (+)-2 was subjected to stereoselective dihydroxylation with OsO 4, resulting in dihydroxy trichloroacetamide (+)-3. The trichloroacetyl group was removed from (+)-3 with aqueous HCl, and the (1R,2R,3S,5R)-3-amino-2-hydroxymethyl-6,6- dimethylbicyclo[3.1.1]heptan-2-ol hydrochloride (-)-4 obtained was transformed to primary, secondary and tertiary aminodiols by reductive amination, N-alkylation of aminodiol (+)-9 and debenzylation of N-benzyl aminodiol (+)-10, respectively. In the reactions of (+)-9 and (+)-14 with formaldehyde, highly regioselective ring closure was observed. In contrast with earlier results, the aminodiols gave pinane-fused oxazolidines (+)-11 and (-)-15. The aminodiols and their oxazolidine derivatives 5-15 were applied as chiral catalysts in the enantioselective addition of diethylzinc to benzaldehyde. The best enantioselectivity was observed in the case of the N-benzyl-substituted derivative (+)-9.

Original languageEnglish
Pages (from-to)144-150
Number of pages7
JournalTetrahedron Asymmetry
Volume23
Issue number2
DOIs
Publication statusPublished - Jan 31 2012

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alkylation
hydrochlorides
formaldehyde
closures
Derivatives
Amination
catalysts
Enantioselectivity
rings
Alkylation
synthesis
Formaldehyde
Catalysts
trichloroacetamide
pinane
diethylzinc
oxazolidine
benzaldehyde
myrtenol

ASJC Scopus subject areas

  • Organic Chemistry
  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Catalysis

Cite this

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title = "Stereoselective synthesis of pinane-type tridentate aminodiols and their application in the enantioselective addition of diethylzinc to benzaldehyde",
abstract = "A library of pinane-based aminodiols were prepared from commercially available (1R)-(-)-myrtenol (-)-1. Compound (-)-1 was transformed into allyl trichloroacetamide (+)-2 via the acetimidate, followed by the Overman rearrangement. In order obtain the aminodiol structure, (+)-2 was subjected to stereoselective dihydroxylation with OsO 4, resulting in dihydroxy trichloroacetamide (+)-3. The trichloroacetyl group was removed from (+)-3 with aqueous HCl, and the (1R,2R,3S,5R)-3-amino-2-hydroxymethyl-6,6- dimethylbicyclo[3.1.1]heptan-2-ol hydrochloride (-)-4 obtained was transformed to primary, secondary and tertiary aminodiols by reductive amination, N-alkylation of aminodiol (+)-9 and debenzylation of N-benzyl aminodiol (+)-10, respectively. In the reactions of (+)-9 and (+)-14 with formaldehyde, highly regioselective ring closure was observed. In contrast with earlier results, the aminodiols gave pinane-fused oxazolidines (+)-11 and (-)-15. The aminodiols and their oxazolidine derivatives 5-15 were applied as chiral catalysts in the enantioselective addition of diethylzinc to benzaldehyde. The best enantioselectivity was observed in the case of the N-benzyl-substituted derivative (+)-9.",
author = "Kinga Csillag and Luk{\'a}cs N{\'e}meth and T. Martinek and Z. Szakonyi and F. F{\"u}l{\"o}p",
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T1 - Stereoselective synthesis of pinane-type tridentate aminodiols and their application in the enantioselective addition of diethylzinc to benzaldehyde

AU - Csillag, Kinga

AU - Németh, Lukács

AU - Martinek, T.

AU - Szakonyi, Z.

AU - Fülöp, F.

PY - 2012/1/31

Y1 - 2012/1/31

N2 - A library of pinane-based aminodiols were prepared from commercially available (1R)-(-)-myrtenol (-)-1. Compound (-)-1 was transformed into allyl trichloroacetamide (+)-2 via the acetimidate, followed by the Overman rearrangement. In order obtain the aminodiol structure, (+)-2 was subjected to stereoselective dihydroxylation with OsO 4, resulting in dihydroxy trichloroacetamide (+)-3. The trichloroacetyl group was removed from (+)-3 with aqueous HCl, and the (1R,2R,3S,5R)-3-amino-2-hydroxymethyl-6,6- dimethylbicyclo[3.1.1]heptan-2-ol hydrochloride (-)-4 obtained was transformed to primary, secondary and tertiary aminodiols by reductive amination, N-alkylation of aminodiol (+)-9 and debenzylation of N-benzyl aminodiol (+)-10, respectively. In the reactions of (+)-9 and (+)-14 with formaldehyde, highly regioselective ring closure was observed. In contrast with earlier results, the aminodiols gave pinane-fused oxazolidines (+)-11 and (-)-15. The aminodiols and their oxazolidine derivatives 5-15 were applied as chiral catalysts in the enantioselective addition of diethylzinc to benzaldehyde. The best enantioselectivity was observed in the case of the N-benzyl-substituted derivative (+)-9.

AB - A library of pinane-based aminodiols were prepared from commercially available (1R)-(-)-myrtenol (-)-1. Compound (-)-1 was transformed into allyl trichloroacetamide (+)-2 via the acetimidate, followed by the Overman rearrangement. In order obtain the aminodiol structure, (+)-2 was subjected to stereoselective dihydroxylation with OsO 4, resulting in dihydroxy trichloroacetamide (+)-3. The trichloroacetyl group was removed from (+)-3 with aqueous HCl, and the (1R,2R,3S,5R)-3-amino-2-hydroxymethyl-6,6- dimethylbicyclo[3.1.1]heptan-2-ol hydrochloride (-)-4 obtained was transformed to primary, secondary and tertiary aminodiols by reductive amination, N-alkylation of aminodiol (+)-9 and debenzylation of N-benzyl aminodiol (+)-10, respectively. In the reactions of (+)-9 and (+)-14 with formaldehyde, highly regioselective ring closure was observed. In contrast with earlier results, the aminodiols gave pinane-fused oxazolidines (+)-11 and (-)-15. The aminodiols and their oxazolidine derivatives 5-15 were applied as chiral catalysts in the enantioselective addition of diethylzinc to benzaldehyde. The best enantioselectivity was observed in the case of the N-benzyl-substituted derivative (+)-9.

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