Lewis Base Catalysis: A Platform for Enantioselective Addition to Alkenes Using Group 16 and 17 Lewis Acids (n → σ*)

Dipannita Kalyani, David J.P. Kornfilt, Matthew T. Burk, Scott E Denmark

Research output: Chapter in Book/Report/Conference proceedingChapter

Abstract

The concept of "Lewis base activation of Lewis acids" has been successfully exploited for the development of myriad catalytic enantioselective reactions, specifically involving Group 14 Lewis acids. Numerous studies have demonstrated the formation of 3C-4E hypervalent bonds between a Lewis base and a Group 16 or 17 Lewis acid. This chapter details the advances in the field of Lewis base-catalyzed enantioselective alkene functionalizations. It presents the advances in seleno-, sulfeno-, and halofunctionalizations, respectively. Electrophilic selenenylation of alkenes is an established method for the rapid introduction of vicinal functional groups often with concomitant formation of rings and stereocenters. This process is characterized by the anti-addition of a nucleophile and selenium electrophile to an isolated double bond. The stereochemical course and mechanism of the electrophilic sulfenylation reaction of alkenes has been studied extensively. By analogy to selenofunctionalization, an "iranium" ion intermediate that preserves the configuration of the alkene is proposed to account for the high antistereospecificity.

Original languageEnglish (US)
Title of host publicationLewis Base Catalysis in Organic Synthesis
PublisherWiley-VCH Verlag
Pages1153-1211
Number of pages59
Volume3
ISBN (Electronic)9783527675142
ISBN (Print)9783527336180
DOIs
StatePublished - Aug 17 2016

Keywords

  • Alkene functionalizations
  • Group 16 Lewis acids
  • Group 17 Lewis acids
  • Halofunctionalization reactions
  • Lewis base catalysis
  • Selenium electrophile
  • Sulfenofunctionalization reactions

ASJC Scopus subject areas

  • Chemistry(all)

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    Kalyani, D., Kornfilt, D. J. P., Burk, M. T., & Denmark, S. E. (2016). Lewis Base Catalysis: A Platform for Enantioselective Addition to Alkenes Using Group 16 and 17 Lewis Acids (n → σ*). In Lewis Base Catalysis in Organic Synthesis (Vol. 3, pp. 1153-1211). Wiley-VCH Verlag. https://doi.org/10.1002/9783527675142.ch24