Benzyne-Mediated Nonconcerted Pathway toward Synthesis of Sterically Crowded [5]- And [7]Oxahelicenoids, Stereochemical and Theoretical Studies, and Optical Resolution of Helicenoids

Prashant M. Gawade, Vaibhav N. Khose, Purav M. Badani, Mohammed Hasan, Sandra Kaabel, Shaikh M. Mobin, Victor Borovkov, Anil V. Karnik*

*Corresponding author for this work

Research output: Contribution to journalArticleScientificpeer-review

7 Citations (Scopus)

Abstract

Synthesis of [5]- and [7]oxahelicenoids via Diels-Alder reaction of sterically crowded bichromenes with benzyne is presented. Studies carried out on Diels-Alder addition product establish the unusual preference for a stepwise mechanism over the concerted reaction pathway. This high yielding general synthetic protocol affords unexpected anti cycloadducts [5]- and [7]oxahelicenoids, as confirmed by crystallographic analysis. To rationalize these intriguing antiaddition products, the reaction mechanism was elucidated by means of DFT analysis. Additionally, hydroxy-functionalized [7]oxahelicenoid has been resolved in its optically pure forms.

Original languageEnglish
Pages (from-to)860-868
Number of pages9
JournalJournal of Organic Chemistry
Volume84
Issue number2
Early online date28 Dec 2018
DOIs
Publication statusPublished - 18 Jan 2019
MoE publication typeA1 Journal article-refereed

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