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Reactions of polycyclic ketones with Dimethoxycarbene; a convenient route for a one-pot preparation of some alpha-hydroxycarboxylic acid esters


Romanski, J; Mloston, G; Heimgartner, H (2007). Reactions of polycyclic ketones with Dimethoxycarbene; a convenient route for a one-pot preparation of some alpha-hydroxycarboxylic acid esters. Helvetica Chimica Acta, 90(7):1279-1288.

Abstract

Polycyclic 'cage' ketones, such as pentacyclo[5.4.0.02,6.03,10.05,9]undecan-8-one (10), pentacyclo[5.4.0.02,6.03,10.05,9]undecane-8,11-dione (11), and adamantan-2-one (16) were treated with the nucleophilic dimethoxycarbene (DMC; 1), which was generated thermally from 2,5-dihydro-2,2-dimethoxy-5,5-dimethyl-1,3,4-oxadiazole (4a) in boiling toluene. In this 'one-pot' procedure, the ahydroxycarboxylic
acid ester 12 or a corresponding derivative 15 or 17 was obtained (Schemes 4 – 7).
Additionally, 'cage' thione 21 was treated with DMC under the same conditions yielding dimethoxythiirane 22 (Scheme 8). Subsequent hydrolysis or desulfurization (followed by hydrolysis on silica gel) of 22 gave alpha-mercaptocarboxylate 25 and the corresponding desulfurized ester 24, respectively. In all cases, the addition of DMC occurred stereoselectively, and the addition from the exo-face is postulated to explain the structures of the isolated products.

Abstract

Polycyclic 'cage' ketones, such as pentacyclo[5.4.0.02,6.03,10.05,9]undecan-8-one (10), pentacyclo[5.4.0.02,6.03,10.05,9]undecane-8,11-dione (11), and adamantan-2-one (16) were treated with the nucleophilic dimethoxycarbene (DMC; 1), which was generated thermally from 2,5-dihydro-2,2-dimethoxy-5,5-dimethyl-1,3,4-oxadiazole (4a) in boiling toluene. In this 'one-pot' procedure, the ahydroxycarboxylic
acid ester 12 or a corresponding derivative 15 or 17 was obtained (Schemes 4 – 7).
Additionally, 'cage' thione 21 was treated with DMC under the same conditions yielding dimethoxythiirane 22 (Scheme 8). Subsequent hydrolysis or desulfurization (followed by hydrolysis on silica gel) of 22 gave alpha-mercaptocarboxylate 25 and the corresponding desulfurized ester 24, respectively. In all cases, the addition of DMC occurred stereoselectively, and the addition from the exo-face is postulated to explain the structures of the isolated products.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:English
Date:2007
Deposited On:04 Nov 2011 12:48
Last Modified:05 Apr 2016 15:04
Publisher:Verlag Helvetica Chimica Acta
ISSN:0018-019X
Funders:Rector of the University of Lodz (grant 505/712), F. Hoffmann-La Roche AG, Basel
Publisher DOI:https://doi.org/10.1002/hlca.200790128

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