Highly Regio- and Stereoselective Intramolecular Rearrangement of Glycidol Acetal to Alkoxy Cyclic Acetals
A new class of highly regio- and stereoselective intramolecular rearrangements of glycidol acetals to produce alkoxylated 1,3-dioxolane/1,3-dioxane is demonstrated. Selective Lewis acid activation of acetal generates an oxocarbenium ion that initiates the epoxide ring-opening event, giving the bicyc...
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| Published in: | Organic letters Vol. 24; no. 33; pp. 6165 - 6170 |
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| Main Authors: | , , |
| Format: | Journal Article |
| Language: | English |
| Published: |
American Chemical Society
26-08-2022
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| Online Access: | Get full text |
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| Summary: | A new class of highly regio- and stereoselective intramolecular rearrangements of glycidol acetals to produce alkoxylated 1,3-dioxolane/1,3-dioxane is demonstrated. Selective Lewis acid activation of acetal generates an oxocarbenium ion that initiates the epoxide ring-opening event, giving the bicyclic [3,1,0]epoxonium ion intermediate that undergoes exo/endo-selective opening by a tethered alkoxide. Mechanistic insights into preferential acetal activation over the epoxide were obtained by crossover experiments. The method was applied in the total synthesis of parvistone B and its 8-ethoxy analogue. |
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| Bibliography: | ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
| ISSN: | 1523-7060 1523-7052 |
| DOI: | 10.1021/acs.orglett.2c02397 |