Rearrangements of the Betulin Core. Synthesis of Terpenoids Possessing the Bicyclo[3.3.1]nonane Fragment by Rearrangement of Lupane-Type Epoxides

Rearrangements of the Betulin Core. Synthesis of Terpenoids Possessing the Bicyclo[3.3.1]nonane Fragment by Rearrangement of Lupane-Type Epoxides

The rearrangements of dihydrobetulin, dihydrobetulinic acid, and abeo-lupane epoxides under acidic conditions (HCl, montmorillonite K10, and BF3·Et2O) were studied. The treatment of dihydrobetulin with HCl or K10 produced abeo-lupane olefins. Their epoxidation afforded epoxides, which, in the presen...

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Veröffentlicht in:Journal of organic chemistry 2021-01, Vol.86 (1), p.1084-1095
Hauptverfasser: Pakulski, Zbigniew, Cmoch, Piotr, Korda, Anna, Luboradzki, Roman, Gwardiak, Katarzyna, Karczewski, Romuald
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container_end_page 1095
container_issue 1
container_start_page 1084
container_title Journal of organic chemistry
container_volume 86
creator Pakulski, Zbigniew
Cmoch, Piotr
Korda, Anna
Luboradzki, Roman
Gwardiak, Katarzyna
Karczewski, Romuald
description The rearrangements of dihydrobetulin, dihydrobetulinic acid, and abeo-lupane epoxides under acidic conditions (HCl, montmorillonite K10, and BF3·Et2O) were studied. The treatment of dihydrobetulin with HCl or K10 produced abeo-lupane olefins. Their epoxidation afforded epoxides, which, in the presence of protic or Lewis acids, rearranged to dienes or lupanes bearing a bicyclo[3.3.1]­nonane fragment. The structure of final products depended on the nature of the catalyst. The HCl promoted 1,4-elimination of water, whereas in the presence of BF3·Et2O bond migration took place preferentially. Montmorillonite K10 favored cyclization to bicyclononane.
doi_str_mv 10.1021/acs.joc.0c02560
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title Rearrangements of the Betulin Core. Synthesis of Terpenoids Possessing the Bicyclo[3.3.1]nonane Fragment by Rearrangement of Lupane-Type Epoxides
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