41031-34-9

Upstream product

• 935-56-8 1-chloroadamantane 
• 6651-36-1 1-(Trimethylsilyloxy)cyclohexene 
• 36960-53-9 1-trimethylsiloxyadamantane 
• 22635-62-7 1-acetyloxyadamantane 
• 768-95-6 1-adamanthanol 
• 768-90-1 1-Adamantyl bromide 
• 108-95-2 phenol 
• 41031-37-2 2-(1-Adamantyl)-cyclohexanol 
• 38614-06-1 2-((3r,5r,7r)-adamantan-1-yl)phenol 

Downstream Products

• 7575-84-0 1-cyclohexyladamantane 

Relevant academic research and scientific papers

Exhaustive One-Step Bridgehead Methylation of Adamantane Derivatives with Tetramethylsilane

A methylation protocol of adamantane derivatives was investigated and optimized using AlCl3 and tetramethylsilane as the methylation agent. Substrates underwent exhaustive methylation of all available bridgehead positions with yields ranging from 62 to 86 %, and up to six methyl groups introduced in one step. Scaling-up of the reaction was demonstrated by performing the >40 gram-scale synthesis of 1,3,5,7-tetramethyladamantane with 62 % yield. For several substrates, rearrangements were observed, as well as cleavage of functional groups or Csp3?Csp2 bonds or even cyclohexyl-adamantyl bonds. Based on mechanistic studies, it is suggested that a reactive methylation complex is formed from tetramethylsilane and AlCl3. X-ray diffraction structures of hexamethylated bis-adamantyls reveal elongation or widening of sp3 carbon bonds between adamantyl moieties to 1.585(3) ? and 125.26(9)° due to repulsive H???H contacts.

Synthesis of Adamantane Derivatives. 59. Reactions of Some Electrophilic Adamantane Derivatives with Unsaturated Organosilanes

1-Adamantyl acetate (5) and 1-adamantyl silyl ether (12) react with unsaturated organosilanes exactly as the chloride 1 does; the reactions of 5 catalyzed by trimethylsilyl triflate and of 12 catalyzed by TiCl4 with 6 and 7 give the corresponding adamantane-substituted products.Under AlCl3-catalyzed conditions, the reactions of 1-adamantylcarbinyl chloride (17) with 6 and 7 give the products which have a homoadamantane skeleton.Interestingly, the reactions of 1-adamantanecarbonyl chloride (22) with α,β- and β,γ-unsaturated silanes proceed smoothly at -78 deg C (TiCl4) or at room temperature (ZnCl2) while the competitive decarbonylation scarcely takes place.Furthermore, the reactions of 22 with silyl enol ethers are efficiently catalyzed with normal Lewis acids such as SnCl4 to give C-adamantanecarbonylated products.Some adamantane-substituted unsaturated silanes are acetylated under the conditions employed for 22 to give structurally related adamantane derivatives.The aldehyde (53) and ketone (54) show different reactivity to the unsaturated organosilanes; the former reacts with 6, 7, and 25 as usual, but the latter does not.

Enones with Strained Double Bonds. 7. Precursors for Substituted Bicyclononane Systems

Compounds 11c, 12, and 13 have been synthesized as potential precursors for the 2-substituted bicyclonon-1(2)-en-3-ones 5 (R = Ph and t-Bu).The lactone 34 and its derivatives 32 have also been synthesized as potential precursors for the parent bicyclo enone 1.

Lewis Acid Mediated α-Alkylation of Carbonyl Compounds, VII. Regio and Position Specific α-tert-Alkylation of Ketones

Structurally different ketones can be alkylated at the α-position via their silyl enol ethers with tert-alkyl halides in the presence of Lewis acids such as titanium tetrachloride (->27 - 35).Concerning the alkylation agent, the position specific introduction of branched and cyclic tert-alkyl groups is possible (->41 - 49).Bridgehead halides of the type 1-adamantyl bromide react analogously (->52 - 61).Silyl enol ethers derived from unsymmetrical ketones react regiospecifically (->63, 64, 66, 67).If the reaction partners contain additional functional groups such as aryl residues (->68, 69) or ester groups (->71) or primary alkyl halides moieties (->73), selectivity in the desired manner is observed. α,α'-Bis-tert-alkylated ketones (74 - 76) are also easily accessible, but not the α,α-isomers.

Synthesis of Adamantane Derivatives. 49. Substitution Reaction of 1-Adamantyl Chloride with Some Trimethylsilylated Unsaturated Compounds

Catalytic substitution reactions at the adamantane bridgehead were studied by using α,β- and β,γ-unsaturated trimethylsilanes.Treatment of 1-adamantyl (Ad) chloride (1) with allyltrimethylsilane and its heteroanalogues, X=Y-Z-SiMe3, in the presence of Lewis acid as a catalyst gave the products Ad-X-Y=Z, X=Y+(Ad)-Z-, and X=Y-Z-Ad, depending on the attack site of the adamantyl group on each X, Y, and Z atom.Treatment of 1 with (phenylethynyl)trimethylsilane also gave a substituted adamantane in good yield.The substitution reactions of 1 with aryl- and heteroaryltrimethylsilanes under similar conditions occurred at a position distinct from that of acetylation, indicating that adamantylation was not influenced by an electronic effect of the trimethylsilyl group.