can be prepared enantiomerically enriched readily. They are extremely useful
chirons for the total asymmetric synthesis of all kinds of natural products and
bioactive compounds such as rare sugars and analogues, monosaccharides, and
disaccharide mimetics. There are several methods for the C–O and C–C bond
cleavage of 7-oxanorbornanes. Because of their bicyclic structure,
7-oxanorbornanes permit to generate a wide chemodiversity in a highly
stereoselective manner.
Keywords 1,4-Cineole • Acid promoted • Aldol reaction • Alkaloid • Antibiotic •
Antitumor • Asymmetric total synthesis • Aza-C-disaccharide • Banyaside • Cantharidin • Carba-pyranose • Carotenoid pigment • C–C bond cleavage • C-disaccharide • C-glycoside • Chiral auxiliary • Conduramine • Conduritol • Cyclization •
Cyclophellitol • Diels–Alder reaction • Diterpenoid • Elimination • Ether cleavage •
Etherification • Ethisolide • Fragrance • Furan • Glycinoeclepin • Heterolysis •
Hexoses • Illudin • Iminodideoxyalditol • Isoavenaciolide • Ketyl radical anion •
Maneonene • Methyl nonactate • Molecular device • “Naked sugars” • Natural
7-oxanorbornanes • Nonactin • Norcantharidin • Palasonin • Peduncularine • Phosphatase inhibitors • Photo-induced reduction • Pinacolic rearrangement • Prostaglandin • Radical reaction • Reduction • Sesquiterpenoid • Single-electron transfer •
Solanoeclepin • Strain of 7-oxanorbornane • Sylvan • Template • Triterpenoid •
Uronolactone
1 Introduction
As other cyclic ethers, unsubstituted 7-oxabicyclo[2.2.1]heptane (1,4-epoxycyclohexane, or 7-oxanorbornane, 1 should be called 7-oxatrinorbornane as three
methyl groups have been removed from the corresponding bornane) and alkylsubstituted derivatives generate useful polymers upon oxa ring openings [1–5]. On
its side, 2-methylidene- 7-oxanorbornane 2 has been used in radical-induced alkene
polymerizations [6, 7]. 7-Oxanorbornane derivatives are found in Nature, some of
these have interesting biological properties, and analogues of these compounds
have also been found to be bioactive [8], for instance, as herbicides [9, 10]. In the
laboratory, 7-oxanorbornanes are readily available through Diels–Alder reactions
of furans or by other methods that will be illustrated. A large number of these
bicyclic templates are available enantiomerically enriched, either through classical
resolution of diastereomers or through asymmetric catalysis [11, 12]. The various
reactions of 7-oxanorbornanes permit a high chemodiversity in organic chemistry
in general and for the synthesis of compounds of biological interest. In addition, the
7-oxanorbornane skeleton allows the construction of unusual templates and molecular devices of interest for biology [13] and material sciences that profit of its shape
and rigidity [14] (Fig. 1).
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A.J. Moreno-Vargas and P. Vogel
chirons for the total asymmetric synthesis of all kinds of natural products and
bioactive compounds such as rare sugars and analogues, monosaccharides, and
disaccharide mimetics. There are several methods for the C–O and C–C bond
cleavage of 7-oxanorbornanes. Because of their bicyclic structure,
7-oxanorbornanes permit to generate a wide chemodiversity in a highly
stereoselective manner.
Keywords 1,4-Cineole • Acid promoted • Aldol reaction • Alkaloid • Antibiotic •
Antitumor • Asymmetric total synthesis • Aza-C-disaccharide • Banyaside • Cantharidin • Carba-pyranose • Carotenoid pigment • C–C bond cleavage • C-disaccharide • C-glycoside • Chiral auxiliary • Conduramine • Conduritol • Cyclization •
Cyclophellitol • Diels–Alder reaction • Diterpenoid • Elimination • Ether cleavage •
Etherification • Ethisolide • Fragrance • Furan • Glycinoeclepin • Heterolysis •
Hexoses • Illudin • Iminodideoxyalditol • Isoavenaciolide • Ketyl radical anion •
Maneonene • Methyl nonactate • Molecular device • “Naked sugars” • Natural
7-oxanorbornanes • Nonactin • Norcantharidin • Palasonin • Peduncularine • Phosphatase inhibitors • Photo-induced reduction • Pinacolic rearrangement • Prostaglandin • Radical reaction • Reduction • Sesquiterpenoid • Single-electron transfer •
Solanoeclepin • Strain of 7-oxanorbornane • Sylvan • Template • Triterpenoid •
Uronolactone
1 Introduction
As other cyclic ethers, unsubstituted 7-oxabicyclo[2.2.1]heptane (1,4-epoxycyclohexane, or 7-oxanorbornane, 1 should be called 7-oxatrinorbornane as three
methyl groups have been removed from the corresponding bornane) and alkylsubstituted derivatives generate useful polymers upon oxa ring openings [1–5]. On
its side, 2-methylidene- 7-oxanorbornane 2 has been used in radical-induced alkene
polymerizations [6, 7]. 7-Oxanorbornane derivatives are found in Nature, some of
these have interesting biological properties, and analogues of these compounds
have also been found to be bioactive [8], for instance, as herbicides [9, 10]. In the
laboratory, 7-oxanorbornanes are readily available through Diels–Alder reactions
of furans or by other methods that will be illustrated. A large number of these
bicyclic templates are available enantiomerically enriched, either through classical
resolution of diastereomers or through asymmetric catalysis [11, 12]. The various
reactions of 7-oxanorbornanes permit a high chemodiversity in organic chemistry
in general and for the synthesis of compounds of biological interest. In addition, the
7-oxanorbornane skeleton allows the construction of unusual templates and molecular devices of interest for biology [13] and material sciences that profit of its shape
and rigidity [14] (Fig. 1).
142
A.J. Moreno-Vargas and P. Vogel