Reactions of heptacyclo[8.4.0.02,12.03,8.04,6.05,9.011,13]tetradecane (binor-s) with acids and alcohols catalyzed by Pd, Rh, and Pt complexes and some transformations of the compounds formed

A new method for the synthesis of diamantane by hydroisomerization of binor-S on treatment with sulfuric acid

“…It should be emphasized that the reaction selectively gives only one of the possible isomers, hydrocarbon 3с , which is confirmed by 1 H and 13 C NMR spectral data. The 13 C NMR spectrum of compound 3с shows five characteristic carbon signals at 33.44, 35.64, 37.84, 38.30, and 40.49 ppm, coinciding with the reported values [ 13 ]. Since 75–80% H 2 SO 4 contains 20–25% water, the participation of water as a hydrogen source in the reaction cannot be ruled out either.…”

“…Attempts to perform hydroisomerization of binor-S ( 2 ) to diamantane ( 1 ) on treatment with nitric or orthophosphoric acid were unsuccessful, with the starting binor-S ( 2 ) being recovered unchanged. The reaction of hydrocarbon 2 with hydrochloric acid proceeds with the addition of HCl to the cyclopropane ring and results in the formation of a mixture of mono- and dichloro derivatives, the synthesis of which has been reported [ 13 – 14 ]. When sulfuric acid is replaced by an ionic liquid prepared from triethylamine and sulfuric acid [ 15 ], the reaction follows a different route: Starting binor-S ( 2 ) is converted to two isomeric hexacyclic hydrocarbons, hexacyclo[8.4.0.0 2,7 .0 3,14 .0 4,8 .0 9,13 ]tetradec-5-ene ( 4а ) and hexacyclo[6.6.0.0.…”

Direct and Stereoselective Iron-Catalyzed Amidation of Binor-S with Alkyl and Aryl Cyanides in Water

“…In this study, the FeCl 3 •6H 2 O-catalyzed Ritter amidation of heptacyclo [8.4.0.0 2,12 .0 3,8 .0 4,6 .0 5,9 .0 11,13 ]-tetradecane (binor-S, 1), incorporating two cyclopropane rings (CPR)in its skeleton, was carried out via addition of organic nitriles (acetonitrile, propionitrile, valeronitrile, benzonitrile) in the presence of water. Other iron compounds tested as catalysts, namely Fe(OAc) 2 •4H 2 O, Fe(acac) 3 , Fe(C 5 H 5 ) 2 , and Fe 2 (CO) 9 , were inactive in this reaction.…”

“…The regioselectivity of cyclopropane ring opening depends crucially on the reactant, catalyst ratio, and on the temperature. Thus, the reaction between binor-S (1) and acetonitrile in the presence of water and FeCl 3 •6H 2 O as catalyst under the developed reaction conditions (FeCl 3 •6H 2 O/1/CH 3 CN/H 2 O = 0.05:1:15:1, 140 °С, 6 h) resulted in quantitative yield of 10-exo-acetamidohexacyclo[9.2.1.0 2,7 .0 3,5 .0 4,8 .0 9,13 ]tetradecane (2) through the selective cleavage of the С4-С5 bond of binor-S (1) (Scheme 2). The amidation of binor-S (1) with benzonitrile, unlike that with aliphatic nitriles, is not selective and affords a 3:1 isomeric mixture of 10-exo-benzamidohexacyclo-[9.2.1.0 2,7 .0 3,5 .0 4,8 .0 9,13 ]tetradecane (6) and 14-benzamidohexacyclo[9.4.0.0 2,7 .0 3,5 .0 4,8 .0 9,13 ]tetradecane (7) in a total yield of 100% (Scheme 5).…”

“…The key role of the iron ion in the reaction is indicated by an experiment in which the reaction of binor-S with a mixture of acetonitrile and water (15:1) was carried out in the presence of 5 mol% HCl for 6 hours, giving compounds 2 and 3 in a 1:5 ratio, with the conversion of binor-S being 30%. 13 On treatment with NaOH in butanol (120 °С, 10 h), amide 2 is hydrolyzed to give 10-exo-aminohexacyclo[9.2.1.0.0 2,7 .0 3,5 .0 4,8 .0 9,13 ]tetradecane (8). When HCl gas is passed through a solution of amine 8 in diethyl ether, hydrochloride 9 is formed.…”