Strained bridgehead cage alcohols and derivatives

Structural elucidation of dioxa‐cage compounds from tetrahydroisobenzofuran‐1(3H)‐one: analysis of NMR data and GIAO chemical shifts calculations

“…91-92°C [54] ). 1 H NMR (300 MHz, CDCl 3 ): δ 1.44 (dm, 1H, H8'); 1.62 (dt, 1H, H8); 2.94 (ddd, 1H, H3a); 3.18-3.23 (m, 1H, H4); 3.26-3.33 (m, 1H, H7); 3.39 (dd, 1H, H7a); 5.02 (bs, 1H, OH); 5.22 (s, 1H, H3); 6.16-6.24 (m, 2H, H5 e H6). 13 A dilute solution of bromine in dichloromethane was added dropwise to a solution of 1 (512.2 mg; 3.08 mmol) in dichloromethane (10 ml) under vigorous stirring until the substrate was fully consumed (about 10 min).…”

“…Over the years, the chemistry and synthesis regarding the polycyclic cage compounds, comprising not only carbocyclic compounds but also heterocyclic analogues, have attracted considerable attention . Their rigid, strained and often symmetric structure provides singular physicochemical properties and bioactivities .…”

“…Over the years, the chemistry and synthesis regarding the polycyclic cage compounds, comprising not only carbocyclic compounds but also heterocyclic analogues, have attracted considerable attention. [1][2][3][4] Their rigid, strained and often symmetric structure provides singular physicochemical properties [5] and bioactivities. [6,7] Besides of being potential substrates for studies of molecular rearrangements [8][9][10] and other reaction mechanisms, [11][12][13] the cage compounds are useful intermediates for the synthesis of more complex molecules, including natural products.…”

Electrochromics by Intramolecular Redox Switching of Single Bonds

“…In 14 and 15, the two carbonyl groups are held in nearly parallel positions; the distance between the two carbon atoms (for 14, 15: d ϭ 260 pm [14] ), however, is too large to form a single bond on reduction, and so no pinacol formation can be observed. [15] In other words, these carbon atoms Figure 6.…”

Recent Reviews

“…Sn2', 66 Aldol reaction, proline-catalyzed, 36 Alkaloids, 138 Alkanes, functionalization, 181 Alkenes, addition, 62 bicyclo[n,1.0], 54 nucleophilic addition to, 136 pyramidalized, 51 synthesis, 156 Alkynes, 108 ligands, 27 Allylsilanes, 165 Aluminum compounds, 122 Amides, proton exchange, 1 Animation, diastereoselective, 103 Amine basicity, effect of strain, 58 Amino acids, N-hydroxy, Biocatalysis, 142 Biomass utilization, 14 Biomimetic transformations, 100 Biomolecular homochirality, 87 Bioorganic chemistry, 176 Biosynthesis, 132 Biotransformations, 168 Bismuth reagents, 65 Boron compounds, 69, 70 Boronic esters, 130 Bridgehead carbocations, 73 Bridgehead enones, 73 C2 symmetry, 72 Cage alcohols, strained, 48 Carbene ligands, 79 Carbocations, a-carbonyl, 147 destabilized, Cumulenes, cyclic, 52,162 Cycloaddition reactions, hetero dienes in, 68 heteroaromatic, 41 Cyclodextrins, as enzyme models, 94 esterolytic activity in, 35 inclusion complexes of, 12 Cyclohexenes, conformational analysis, 194 Cyclopentadienyl carbonyl complexes, 28 Cyclopentanoids, 64 Cyclopropanes, optically active, 60 Cycloproparenes, 55 -Delocalization, 125 Deoxyvalenol derivatives, 132 Dianions, conjugated, 125 Diastereoselective amination, 103 Diels-Alder reaction, 163 inverse electron demand, 167 Dihydropyrenes, 159 1,4-Dioxene, 99 Dioxiranes,…”