Cage opening and rearrangement of 1-iodocubane-4-carboxaldehyde

Photoinduced nucleophilic substitution of iodocubanes with arylthiolate and diphenylphosphanide ions. Experimental and computational approaches

“…Potassium tert -butoxide, 4-methoxybenzenethiol (3), benzenethiol (4), naphthalene-2-thiol (11) and potassium diphenylphosphide solution (0.5 M in THF) are commercially available and used as received. Methyl-4-iodocubane-1-carboxylate (1) and 1,4-diiodocubane (2) were synthesized according to ref. 18 .…”

“… 17 They have not experienced any cage/rearrangement or cage opening/fragmentation reactions as is well-known to occur for iodinated cubane analogues. 18 Therefore, each one was separately exposed to reactions with S- and P-centered anions, under eT conditions. Notably, the sulfur 7 c ,19 or phosphine 7 c cubane derivatives are not a recurrent motif in the current literature.…”

Cubane: 50 Years Later

“…Instead observed a mixture of 4-iodocubanecarboxylic acid (140), 1-iodo-4-(hydroxymethyl)cubane (141), benzaldehyde (142), benzylalcohol (143), benzoic acid (144), and benzyl benzoate (145; Scheme 39). 110 The authors explained that the formation of products 140 and 141 are simply those of a Cannizaro reaction of the aldehyde 137, 113 The authors mention that this would be called "trans in a five-membered ring. "…”

“…Rearrangement of Cubane (1) to Cuneane (136) 106 Scheme 38. Dipolar Character of 4-Iodocubane-1-carboxyaldehyde () 110 Scheme 39. Thermolysis of 4-Iodocubane-1-carboxaldehyde (137) 110 Chemical Reviews Review DOI: 10.1021/cr500523x Chem.…”

Evaluation of a chiral cubane-based Schiff base ligand in asymmetric catalysis reactions

“…Spontaneous cage opening has been observed with cubanol yielding vinylcyclobutenylketene [13–14], whereas dicubyl disulfide is remarkably stable [15]. More recently, 4-iodo-1-vinylcubane was shown to undergo cage opening/rearrangement to form 4-vinyl- trans -β-iodostyrene [16–17], whereas 1-iodocubane-4-carboxaldehyde undergoes cage opening/fragmentation to afford benzaldehyde, which further reacts to give benzyl benzoate [18]. …”