Ring contraction and ring expansion reactions in terpenoid biosynthesis and their application to total synthesis

• Nicolas Kratena,
• Nicolas Heinzig and
• Peter Gärtner

Beilstein J. Org. Chem. 2026, 22, 289–343, doi:10.3762/bjoc.22.21

Unveiling the regioselectivity of rhodium(I)-catalyzed [2 + 2 + 2] cycloaddition reactions for open-cage C₇₀ production

• Cristina Castanyer,
• Anna Pla-Quintana,
• Anna Roglans,
• Albert Artigas and
• Miquel Solà

Beilstein J. Org. Chem. 2024, 20, 272–279, doi:10.3762/bjoc.20.28

• reaction between diynes and C60, followed by a cage-opening through a Rh‐catalyzed di‐π‐methane rearrangement (Scheme 1). It is well-known that [6,6]-bonds (the bonds at the junction between two six-membered rings, Figure 1, left) are more reactive than [5,6]-bonds in C60 [36][37][38], and, not

One hundred years of benzotropone chemistry

• Arif Dastan,
• Haydar Kilic and
• Nurullah Saracoglu

Beilstein J. Org. Chem. 2018, 14, 1120–1180, doi:10.3762/bjoc.14.98

Effects of anion complexation on the photoreactivity of bisureido- and bisthioureido-substituted dibenzobarrelene derivatives

• Heiko Ihmels and
• Jia Luo

Beilstein J. Org. Chem. 2011, 7, 278–289, doi:10.3762/bjoc.7.37

• . Direct irradiation of the ureido-substituted derivative induces a di-π-methane rearrangement to the corresponding dibenzosemibullvalene derivative, whereas the thioureido-substituted derivative is almost photoinert. Complexes of the latter derivative with chloride, carboxylates, or sulfonate anions

• formation of the dibenzosemibullvalene with moderate stereoselectivity (68:32 er). In contrast, the thioureido derivative showed no such effect upon complexation of chiral anions. Keywords: dibenzobarrelenes; dibenzosemibullvalenes; di-π-methane rearrangement; supramolecular photochemistry; (thio)urea

• benzophenone, a triplet-state di-π-methane rearrangement is induced. Thus, in the initial reaction step connection between one vinyl and one benzo carbon atom takes place, i.e., a so called vinyl–benzo bridging, that leads to the intermediate biradical BR1a [29]. Subsequent rearomatization with the formation

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

• Heiko Ihmels and
• Jia Luo

Beilstein J. Org. Chem. 2011, 7, 119–126, doi:10.3762/bjoc.7.17

• ], 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; Introduction The di-π-methane (DPM) rearrangement is among

Synthesis and Diels–Alder cycloaddition reaction of norbornadiene and benzonorbornadiene dimers

• Bilal Nişancı,
• Erdin Dalkılıç,
• Murat Güney and
• Arif Daştan

Beilstein J. Org. Chem. 2009, 5, No. 39, doi:10.3762/bjoc.5.39

• compounds are of great scientific interest because of their unusual geometry and high reactivity. For example, these compounds exhibit a unique behavior in the cationic Wagner–Meerwein rearrangement [1][2][3][4][5][6][7][8][9][10], in the solvolytic reactivity [11], in the photochemical di-π-methane

• rearrangement [12][13][14][15], as well as in other instances [16][17][18][19][20][21][22]. Therefore, functionalizations of these compounds are important. In this study, we investigated the synthesis and Diels–Alder cycloaddition reaction of norbornadiene and benzonorbornadiene dimers. Results and Discussion