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uick Search Title, abstract, keywords Author  Preite e.g. j s smith

Journal/book title Volume Issue Page  

13 of 15 Tetrahedron: Asymmetry 

Volume 4, Issue 1 , January 1993, Pages 17-20

oi:10.1016/S0957-4166(00)86006-1 opyright © 1993 Published by Elsevier Science Ltd. All rights reserved.

Communications

Resolution and absolute configuration of a tricyclic

actone. A potentially useful precursor of highly

functionalized terpenoids*1

Marcelo D. Preite , Juan Zinczuk, María I. Colombo, José A. Bacigaluppo, Manuel

González-Sierra and Edmundo A. Rúveda, * 

nstituto de Química Orgánica de Síntesis (CONICET-UNR) Facultad de Ciencias Bioquímicas y Farmacéuticas, Casilla deCorreo 991, 2000 Rosario, Argentina

Received 16 November 1992. Available online 20 March 2001.

Abstract

The highly functionalized tricyclic lactone 1 was obtained in optically pure form by thesulfoximine-mediated resolution of the enone methyl acetal 3. The absolute configuration of (−)-3 and consequently of (+)-1, was determined by the transformation of (−)-3 into (−)-5, aknown intermediate in the total synthesis of forskolin ( 2) and confirmed by application of the high field FT NMR Mosher method to alcohol 6.

Graphical AbstractEnantiomerically pure (−)-3 was obtained by a sulfoximine assisted resolution. From (−)-3the tricyclic lactones (+)-1 and (−)-5 were then prepared. The absolute configuration of these optically active compounds was confirmed by application of the high field FT NMRMosher method to alcohol (−)-6 

(3K)

LogRe

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Stereochemistry Abstract

2aβ,3,5aα,6,7,8,8aβ,8b-Octahydro-6,6,8bβ-trimethyl-3-oxo-2H-napthanol[1,8-bc]furan-2-ona

C14H18O3

E.e.> 95% by 1H NMR in the presence of tris(3-[heptafluoro propyl-hydroxymethylene]-d -camphorato)

αD = +4.36 (c = 0.78, CHCl3

Source of chirality: sulfoximine assistedresolution

Absolute configuration 1S ,5S ,9S ,10S (determined by high field NMR application of the Mosher method)

2aβ,3,5aα,6,7,8,8aβ,8b-Octahydro-2β-methoxy-6,6,8bβ-trimethyl-3-oxo-2H-napthanol[1,8-bc]furan

C15H22O3

E.e.> 95% by 1H NMR in the presence of tris

(3-[heptafluoro propyl-hydroxymethylene]-d -camphorato)

αD = −141.3 (c = 0.47, CHCl3

Source of chirality: sulfoximine assistedresolution

Absolute configuration 1S ,5S ,9 R,10S ,11 R(determined by high field NMR application of the Mosher method)

2aβ,5,5aα,6,7,8,8aβ,8b-Octahydro-3,6,6,8bβ-tetramethyl-5-oxo-2H-napthanol[1,8-bc]furan-2-ona

C15H20O3

E.e.> 95% by 1H NMR in the presence of tris(3-[heptafluoro propyl-hydroxymethylene]-d -camphorato)

αD = −42.7 (c = 0.37, CHCl3

Source of chirality: sulfoximine assistedresolution

Absolute configuration 1S ,5S ,9S ,10S (determined by high field NMR application of 

the Mosher method)

2a ,3,5aα,6,7,8,8a ,8b-Octah dro-3α-

E.e.> 95% by 1H NMR analysis of theMTPA (Mosher) ester

αD = −170 (c = 2.38, acetone)

Source of chirality: sulfoximine assistedresolution

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hydroxy-2β-methoxy-6,6,8bβ-trimethyl-2H-napthanol[1,8-bc]furan

C15H24O3

Absolute configuration 1S ,5S ,8 R,9S ,10S ,11 Rdetermined by high field NMR application of the Mosher method)

*1 This paper is dedicated to Professor Alan R. Battersby for his decades of contribution toOrganic Chemistry and to commemorate his retirement in 1992.

Tetrahedron: Asymmetry 

Volume 4, Issue 1 , January 1993, Pages 17-20

 13 of 15 

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