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. 2011 Jan 26:7:119-26.
doi: 10.3762/bjoc.7.17.

Synthesis of cationic dibenzosemibullvalene-based phase-transfer catalysts by di-π-methane rearrangements of pyrrolinium-annelated dibenzobarrelene derivatives

Heiko Ihmels  1 , Jia Luo
Affiliations

Synthesis of cationic dibenzosemibullvalene-based phase-transfer catalysts by di-π-methane rearrangements of pyrrolinium-annelated dibenzobarrelene derivatives

Heiko Ihmels et al. Beilstein J Org Chem. .

Abstract

Dibenzobarrelene derivatives, that are annelated with a pyrrolinium unit [N,N-dialkyl-3,4-(9',10'-dihydro-9',10'-anthraceno-3-pyrrolinium) derivatives], undergo a photo-induced di-π-methane rearrangement upon triplet sensitization to give the corresponding cationic dibenzosemibullvalene derivatives [N,N-dialkyl-3,4-{8c,8e-(4b,8b-dihydrodibenzo[a,f]cyclopropa[cd]pentaleno)}pyrrolidinium derivatives]. Whereas the covalent attachment of a benzophenone functionality to the pyrrolinium nitrogen atom did not result in an internal triplet sensitization, the introduction of a benzophenone unit as part of the counter ion enables the di-π-methane rearrangement of the dibenzobarrelene derivative in the solid-state. Preliminary experiments indicate that a cationic pyrrolidinium-annelated dibenzosemibullvalene may act as phase-transfer catalyst in alkylation reactions.

Keywords: di-π-methane rearrangement; dibenzobarrelenes; dibenzosemibullvalenes; phase-transfer catalysis; photochemistry; polycylic compounds.

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Figures

Scheme 1
Scheme 1
Photorearrangements of dibenzobarrelene (DBB).
Figure 1
Figure 1
General structure of pyrrolidinium-annelated dibenzosemibullvalenes (pyDBS).
Scheme 2
Scheme 2
Synthesis of dibenzobarrelene derivatives 2a–g.
Scheme 3
Scheme 3
Di-π-methane rearrangements of dibenzobarrelene derivatives 2a–f (counter ions omitted for clarity).
Scheme 4
Scheme 4
Di-π-methane rearrangement of dibenzobarrelene derivative 2g.
Scheme 5
Scheme 5
Synthesis and solid-state photoreactivity of the sulfonate salt 2b-4.
Scheme 6
Scheme 6
Phase-transfer catalyzed alkylation reactions (see Table 1 for details).
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