58008-54-1

Upstream product

• 58008-63-2 pentacyclo<5.3.1.0^2,6.0^3,5.0^4,9>undecane 
• 77419-19-3 tetracyclo<5.3.1.0^2,6.0^4,9>undecane-3,5-dione 
• 92285-08-0 C₁₂H₁₄ClORh*CO 
• 77419-12-6 Tetracyclo<5.3.1.0^2,6.0^4,9>undecan-3-one 
• 77419-17-1 endo,exo-3,5-dihydroxytetracyclo<5.3.1.0^2,6.0^4,9>undecane 
• 77480-47-8 endo-tetracyclo<5.3.1.0^2,6.0^4,9>undecan-3-ol 

Relevant academic research and scientific papers

Noriceane (Tetracyclo2,6.04,9>undecane) and 3,5-Dehydronoriceane (Pentacyclo2,6.03,5.04,9>undecane)

Heating a mixture of endo, exo- and endo, endo-2,4-dibromohomoadamantanes at 180 deg C in hexamethylphosphoric triamide (HMPT) brings about a novel skeletal rearrangement with concomitant dehydrobromination to give tricyclo4,9>undeca-2,5-diene (5) in 88percent yield.Direct photoexcitation of 5 in diethyl ether induces an intramolecular cycloaddition to produce 3,5-dehydronoriceane (2).The bicyclopentane moiety constrained in the cage structure of 2 shows almost the same 13C-H coupling constants as those of bicyclopentane itself.Finally hydrogenation of 2 over PtO2 easily proceeds to afford noriceane, which is named after the structure of iceane.

Synthesis of 3-Mono- and 3,5-Difunctionalized Noriceanes (Tetracyclo2,6.04,9>undecanes via Oxymetallation of 3,5-Dehydronoriceane (Pentacyclo2,6.03,5.04,9>undecane). Oxidation of Bicyclopentane System by Mercury(II), Thallium(III), and Lead(IV) Acetates

Oxymercuration of 3,5-dehydronoriceane (1) followed by sodium borohydride reduction gives exclusively endo-3-noriceanol in 80 percent yield.The trans-1,3--addition organomercury intermediate is isolated as endo-3-acetoxy-exo-5-(chloromercurio)noriceane.Oxidation of 1 with thallium(III) acetate gives three diacetates, exo,exo- and endo,exo-3,5-diacetoxynoriceanes and endo,exo-4,5-diacetoxytetracyclo2,6.03,9>undecane (11) in a ratio of 6:61:27 in 68percent combined yield.The analogous oxidation of 1 with lead(IV) acetate gives 9, 10, and 11 in a ratio of 50:25:25 in 80percent combined yield.On the basis of the stereochemistry of the products as well as the products distribution, we propose that 1,3-bridged metanol ion intervenes and plays an important role in the oxymetallation reaction of bicyclopentane system.

Reaction of 3,5-Dehydronoriceane with Tetracarbonylbis(μ-chloro)dirhodium : Evidence for the Oxidative Addition of Rh(I) Complex to a Bicyclopentane System

A stoichiometric reaction of the title compound (1) with Rh2(CO)4Cl2 gives a stable acylrhodium complex (3).This is the first experimental evidence for the oxidative addition of Rh(I) complex to a bicyclopentane system.Treatment of 3 with 2 equiv of triphenylphosphine gives rise to the starting bicyclopentane (1), instead of a keto compound.This contrasts markedly with reactions of acylrhodium complexes derived from other strained systems with triphenylphosphine to yield ketones.The structure of 3 is further confirmed by hydride reduction of 3 affording exo-3-(hydroxymethyl)noriceane (8), along with a small amount of two hydrocarbons, noriceane (9) and exo-3-methylnoriceane (10).