Cucurbituril adamantanediazirine complexes and consequential carbene chemistry

Shipra Gupta, Rajib Choudhury, Daniel Krois, Udo H. Brinker, Vaidhyanathan Ramamurthy

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

Adamantanediazirines, precursors of adamantanylidenes, form 1:1 complexes (guest to host) with cucurbit[7]uril and cucurbit[8]uril and a 3:1 complex with a Pd nanocage in water. 1H NMR spectra suggested that these complexes are stable in water on the NMR time scale. While photolysis of adamantanediazirines in water gave mainly adamantanone and adamantanol via adamantanylidene as intermediate, the 1:1 complexes of adamantanediazirine with cucurbiturils gave intramolecular C-H insertion products of adamantanylidene in >90% yield. The study establishes that significant control of carbene reactivity can be achieved when the precursor is encapsulated within a tight inert cavity. While the general characteristics of molecular containers can be understood on the basis of concepts such as "confinement" and "weak interactions", each one is unique and deserves careful scrutiny.

Original languageEnglish
Pages (from-to)5155-5160
Number of pages6
JournalJournal of Organic Chemistry
Volume77
Issue number11
DOIs
StatePublished - Jun 1 2012

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Water
Nuclear magnetic resonance
Photolysis
Containers
cucurbituril
carbene
adamantanone
cucurbit(7)uril
cucurbit(8)uril

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Cucurbituril adamantanediazirine complexes and consequential carbene chemistry. / Gupta, Shipra; Choudhury, Rajib; Krois, Daniel; Brinker, Udo H.; Ramamurthy, Vaidhyanathan.

In: Journal of Organic Chemistry, Vol. 77, No. 11, 01.06.2012, p. 5155-5160.

Research output: Contribution to journalArticle

Gupta, Shipra ; Choudhury, Rajib ; Krois, Daniel ; Brinker, Udo H. ; Ramamurthy, Vaidhyanathan. / Cucurbituril adamantanediazirine complexes and consequential carbene chemistry. In: Journal of Organic Chemistry. 2012 ; Vol. 77, No. 11. pp. 5155-5160.
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