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Carbonyl Transposition and Regio- and Stereo-specific Syntheses of New Alcohols, Amino-alcohols, and Ketones in the Monoterpenoid 1,3,3-Trimethyl-2-oxabicyclooctane

DOI: 10.1039/P19800002626

Source and publish data:

Journal of the Chemical Society. Perkin transactions I p. 2626 - 2630 (1980)

Update date:2022-08-04

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Authors:

Bondavalli, FrancescoBondavalli, Francesco

Schenone, PietroSchenone, Pietro

Ranise, AngeloRanise, Angelo

Lanteri, SilviaLanteri, Silvia

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Article abstract of DOI:10.1039/P19800002626

An efficient transposition of carbonyl group R1-CO-CH2-R2 -> R1-CH2-CO-R2 in the 1,3,3-trimethyl-2-oxabicyclo<2.2.2>octane system was carried out via hydroboration-oxidation of 6-dialkylamino-1,3,3-trimethyl-2-oxabicyclo<2.2.2>oct-5-enes (3a-c), which gave regio- and stereo-specifically 6-cis-dialkylamino-1,3,3-trimethyl-2-oxabicyclo<2.2.2>octan-5-trans-ols (4a-c) in high yield.Cope reaction on the N-oxide (5b) obtained from the amino-alcohol (4b) with hydrogen peroxide led to 1,3,3-trimethyl-2-oxabicyclo<2.2.2>octan-5-one (6), the other possible isomer of the long-known 1,3,3-trimethyl-2-oxabicyclo<2.2.2>octan-6-one (1b).The ketone (6) was also obtained from 1,3,3-trimethyl-2-oxabicyclo<2.2.2>oct-5-ene (2) via its trans-epoxide (11), lithium aluminium hydride reduction at 160-165 deg C of which gave stereo- and regio-specifically 1,3,3-trimethyl-2-oxabicyclo<2.2.2>octan-5-trans-ol (9b).Chromic acid oxidation of (9b) and (4a-c) under various conditions gave the ketone (6) and the amino-ketones (7a-c), respectively.Lithium aluminium hydride reduction of (6) and (7a-c) afforded stereospecifically the cis-alcohol (9a) and 6-cis-dialkylamino-1,3,3-trimethyl-2-oxabicyclo<2.2.2>octan-5-cis-ols (8a-c), respetively.Hydroboration-oxidation of the alkene (2) was not regiospecific, giving a 3:1 mixture of the trans-alcohols (9b) and (10b), respectively.

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Product name:(1R,4R,5R,6S)-1,3,3-trimethyl-6-(pyrrolidin-1-yl)-2-oxabicyclo[2.2.2]octan-5-ol

Cas No:76735-19-8

76735-19-8

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