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Synthesis 2001(9): 1395-1405
DOI: 10.1055/s-2001-15231
PAPER
© Georg Thieme Verlag Stuttgart · New York

Synthesis of Enantiomerically Pure 1,5,7-Trimethyl-3-azabicyclo[3.3.1]nonan-2-ones as Chiral Host Compounds for Enantioselective Photochemical Reactions in Solution

Thorsten Bach*a, Hermann Bergmannb, Benjamin Groscha, Klaus Harmsb, Eberhardt Herdtweckc
a Technische Universität München, Lehrstuhl für Organische Chemie I, Lichtenbergstr. 4, 85747 Garching, Germany
b Philipps-Universität Marburg, Fachbereich Chemie, 35032 Marburg, Germany
c Technische Universität München, Lehrstuhl für Anorganische Chemie, Lichtenbergstr. 4, 85747 Garching, Germany
Fax: +49(89)28913315; e-Mail: thorsten.bach@ch.tum.de;
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Publikationsverlauf

Received 5 February 2001
Publikationsdatum:
29. September 2004 (online)

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Abstract

The synthesis of the title compounds is described. As common starting material, 1,5,7-trimethyl-2,4-dioxo-3-azabicyclo[3.3.1]-nonan-7-carboxylic acid chloride (4) was employed which is in turn available from cis,cis-1,3,5-trimethylcyclohexane-1,3,5-tricarboxylic acid (Kemp’s triacid). For the synthesis of the diastereomeric menthyl esters 1 and 2, the chloride 4 was initially substituted by (-)-menthol and its imide part was subsequently reduced to an amide by consecutive treatment with sodium borohydride and triethylsilane. The enantiomerically pure hosts 3a and 3b were obtained from the racemate by resolution of their N-menthoxycarbonyl derivatives. The racemic compounds rac-3a and rac-3b were prepared from the acid chloride 4 and the ortho-hydroxyanilines 9a and 9b via amide formation, condensation to the oxazole and reduction. Structural data are provided which prove the absolute configuration of compound ent-3b and the relative configuration of compound rac-3a.

Key words

supramolecular chemistry - amides - enantiomeric resolution - reductions - photochemistry

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    To whom inquiries about the X-ray analysis of compound ent-3b should be addressed at the Technische Universität München

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11

5: C22H35NO4; Crystal Data: colorless prism; rhombohedral, R3, a = b = 2822.4(1)pm, c = 1526.2(1)pm; Z = 6; R = 5.16%; GOF = 1.034. Data collection: Data were collected on an Enraf Nonius CAD4 instrument at 293 K employing Cu Kα irradiation (154.178 pm). ω-scan, 6287 reflections (-h, +k, ±l), Θmax = 65°, 5754 independent and 4128 observed reflections [F ≥ 4σ(F)], 521 refined parameters, wR2 = 0.1373, residual electron density 0.174 eÅ-3, direct methods, hydrogen atoms calculated. Further details of the crystal structure investigations related to this compound may be obtained from the Director of the Cambridge Crystallographic Data Centre, 12 Union Road, GB-Cambridge CB2 1EZ, on quoting the full literature citation (CCDC-157021)

20

rac-3a: C22H24N2O2; Crystal Data: yellowish prism; monoclinic, P21/c, a = 1137.2(2)pm, b = 1491.2(1)pm, c = 1154.5(3)pm; β = 111.7(2)°; Z = 4; R = 6.49%; GOF = 1.044. Data collection: Data were collected on an Enraf Nonius CAD4 instrument at 223 K employing Cu Kα irradiation (154.178 pm), ω-scan, 2410 reflections (±h, +k, ±l), Θmax = 55°, 2276 independent and 1659 observed reflections [F ≥ 4σ(F)], 242 refined parameters, wR2 = 0.2057, residual electron density 0.225 eÅ-3. The structure was resolved by direct methods with carbon bound hydrogen atoms calculated and N-H atom refined. Further details of the crystal structure investigations related to this compound may be obtained from the Director of the Cambridge Crystallographic Data Centre, 12 Union Road, GB-Cambridge CB2 1EZ, on quoting the full literature citation (CCDC-157022)