A Mechanistically Inspired Halenium Ion Initiated Spiroketalization: Entry to Mono- and Dibromospiroketals
Dr. Kumar Dilip Ashtekar
Cancer Biology Institute, Yale School of Medicine, West Haven, Connecticut, 06516 USA
These authors contributed equally to this work.
Search for more papers by this authorDr. Hadi Gholami
Department of Chemistry, Michigan State University, East Lansing, MI 48824 USA
These authors contributed equally to this work.
Search for more papers by this authorMehdi Moemeni
Department of Chemistry, Michigan State University, East Lansing, MI 48824 USA
Search for more papers by this authorAnkush Chakraborty
Department of Chemistry, Michigan State University, East Lansing, MI 48824 USA
Search for more papers by this authorLindsey Kiiskila
Department of Chemistry, Michigan State University, East Lansing, MI 48824 USA
Search for more papers by this authorDr. Xinliang Ding
Department of Chemistry, Michigan State University, East Lansing, MI 48824 USA
Search for more papers by this authorEdmond Toma
Department of Chemistry, Michigan State University, East Lansing, MI 48824 USA
Search for more papers by this authorChristopher Rahn
Department of Chemistry, Michigan State University, East Lansing, MI 48824 USA
Search for more papers by this authorCorresponding Author
Prof. Dr. Babak Borhan
Department of Chemistry, Michigan State University, East Lansing, MI 48824 USA
Search for more papers by this authorDr. Kumar Dilip Ashtekar
Cancer Biology Institute, Yale School of Medicine, West Haven, Connecticut, 06516 USA
These authors contributed equally to this work.
Search for more papers by this authorDr. Hadi Gholami
Department of Chemistry, Michigan State University, East Lansing, MI 48824 USA
These authors contributed equally to this work.
Search for more papers by this authorMehdi Moemeni
Department of Chemistry, Michigan State University, East Lansing, MI 48824 USA
Search for more papers by this authorAnkush Chakraborty
Department of Chemistry, Michigan State University, East Lansing, MI 48824 USA
Search for more papers by this authorLindsey Kiiskila
Department of Chemistry, Michigan State University, East Lansing, MI 48824 USA
Search for more papers by this authorDr. Xinliang Ding
Department of Chemistry, Michigan State University, East Lansing, MI 48824 USA
Search for more papers by this authorEdmond Toma
Department of Chemistry, Michigan State University, East Lansing, MI 48824 USA
Search for more papers by this authorChristopher Rahn
Department of Chemistry, Michigan State University, East Lansing, MI 48824 USA
Search for more papers by this authorCorresponding Author
Prof. Dr. Babak Borhan
Department of Chemistry, Michigan State University, East Lansing, MI 48824 USA
Search for more papers by this authorIn memory of Ghazal Nourian and other students lost on Ukrainian Flight 752
Abstract
Employing halenium affinity (HalA) as a guiding tool, the weak nucleophilic character of alkyl ketones was modulated by the templating effect of a tethered 2-tetrahydropyranyl(THP)-protected alcohol towards realizing a bromenium ion initiated spiroketalization cascade. Addition of ethanol aided an early termination of the cascade by scavenging the THP group after the halofunctionalization stage, furnishing monobromospiroketals. Alternatively, exclusion of ethanol from the reaction mixture biased the transient oxocarbenium towards α-deprotonation that precedes a second bromofunctionalization event thus, furnishing dibrominated spiroketals. The regio- and stereoselectivity exploited in the current methodology provides a novel and rapid access to the dibrominated spiroketal motifs exhibited by several natural products.
Open Research
Data Availability Statement
The data that support the findings of this study are available in the Supporting Information of this article.
Supporting Information
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| Filename | Description |
|---|---|
| ange202115173-sup-0001-12a.cif16 KB | Supporting Information |
| ange202115173-sup-0001-15.cif311.5 KB | Supporting Information |
| ange202115173-sup-0001-8c.cif181.9 KB | Supporting Information |
| ange202115173-sup-0001-9c.cif182.2 KB | Supporting Information |
| ange202115173-sup-0001-Calculation_of_HalA_values.xlsx16.1 KB | Supporting Information |
| ange202115173-sup-0001-Coordinates-DFT.pdf2.8 MB | Supporting Information |
| ange202115173-sup-0001-misc_information.pdf6.9 MB | Supporting Information |
Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.
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