Nortricyclanols

N-Nitroso N phenylglycine, 46, 96 reaction with acetic anhydride to yield 3 phenylsydnone, 46, 96 Nitrosyl chloride, addition to bicyclo-[2 2 ljhepta 2,5 diene, 46, 75 2,4-Nonanedione, 47, 92 Nonane, 1,1,3 trichloro-, 46,104 Nortricyclanol, 46, 74 oxidation by chromic acid, 46, 78 Nortricyclanone, 46, 77 Nortncj clyl acetate 46, 74 frombicyclo[2 2 ljhepta 2,5 dieneand acetic acid, 46, 74 saponification of, 46, 75... 

Whereas exo-norbornene oxide rearranges to nortricyclanol on treatment with strong base through transannular C-H insertion (Scheme 5.11), endo-norbornene oxide 64 gives norcamphor 65 as the major product (Scheme 5.14) [15, 22]. This product arises from 1,2-hydrogen migration very little transannular rearrangement is observed. These two reaction pathways are often found to be in competition with one another, and subtle differences in substrate structure, and even in the base employed, can have a profound influence on product distribution. 

The addition of carboxylic acids to bicyclo[2.2.1]hepta-2,5-diene has been described by several authors the method described here is a modification of these procedures. Nortricyclanol has been prepared by the hydration of bicyclo[2.2.1]hepta-2,5-diene and the solvolysis of nortricyclyl and bicyclo[2.2.1]hept-2-en-5-yl halides, as well as by the saponification and... 

The preparation of nortricyclanol is described in this volume, p. 74. The crude, unsublimed nortricyclanol is a satisfactory starting material. 

The present preparation affords high-purity nortricyclanol in good yield without the necessity of tedious purification. It illustrates a convenient way to convert olefins to alcohols and to remove olefinic impurities from alcohols. Nortricyclanol is of current interest in studies of highly strained ring systems. It is readily oxidized to nortricyclanone. ... 

The complex Mo(tfd)3 was reported by King and co-workers (86) to catalyze the conversion of quadricyclane to norbornadiene (Eq. 9), polymerization of quadricyclane or norbornadiene, as well as the addition of water to quadricyclane to give nortricyclanol (Eq. 15). The reactions appear to involve pseudo-[4 + 2] cycloaddition to the sulfur atoms in the dithioketone form of the metal... 

The classical isomerization of jco-norbornene oxide 82 to nortricyclanol 83 <1964JOC2830> was next examined (Scheme 38) chiral lithium amides or organolithium/(—(-sparteine complexes effected this transformation, with up to 52% ee <1996TA1275>. 

Stereochemical studies have brought an important contribution to the radical mechanism of the boro-hydride reduction of organomercurials. A recent H NMR study of the reduction of norbomyl-type mercurials with NaBD4 confirmed the previous finding of Gray and Jackson about the composition of the product mixture. The major components were clearly nortricyclanol and anti-7-norbomeol. H NMR data provided accurate measures of the preferred directions of deuterium abstraction by the radical intermediate. ... 

Remote double bonds often participate in epoxide openings, sometimes with extensive skeletal changes. ejco-Norbomadiene oxide (15 equation 6) provides an interesting example. Meinwald et alP found that this very acid-sensitive material rearranged simply on standing to give the endo-aldehyde (17), presumably via the intermediate nortricyclanol ion (16). 

Clearly, the presence of azine 53 and di-3-nortricyclyl ether (3-(tricyclo[2.2.1.02,6]hep-tan-3-yloxy)tricyclo[2.2.1.02,6]heptane, 56) after photolysis of the 45 NaY FAU IC demonstrates that some bimolecular reactions occurred. The diffusion of ephemeral carbene 46 within the multicameral lattice was thus indicated. The principal formation of 3-nortricyclanol (tricyclo[2.2.1.02 6]heptan-3-ol, 55f) validates that a significant amount of water still remains inside NaY even after thermal activation. 

Meinwald et al. recommend this method for oxidation of nortricyclanol (3) to... 

Norbornene epoxide (1) is isomerized by this strongly basic reagent cleanly if in only moderate yield to nortricyclanol (2). Acid catalysts act on (1) to give mixtures of products. 

D. M. Hodgson, R. Wisedale, Enantioselective rearrangement of exo-norbornene oxide to nortricyclanol, Tetrahedron Asymm. 7 (1996) 1275. 

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