74203-38-6Relevant academic research and scientific papers
Experimental and Computational Mechanistic Investigation of Chlorocarbene Additions to Bridgehead Carbene-Anti-Bredt Systems: Noradamantylcarbene-Adamantene and Adamantylcarbene-Homoadamantene
Hare, Stephanie R.,Orman, Marina,Dewan, Faizunnahar,Dalchand, Elizabeth,Buzard, Camilla,Ahmed, Sadia,Tolentino, Julia C.,Sethi, Ulweena,Terlizzi, Kelly,Houferak, Camille,Stein, Aliza M.,Stedronsky, Alexandra,Thamattoor, Dasan M.,Tantillo, Dean J.,Merrer, Dina C.
, p. 5049 - 5065 (2015)
Cophotolysis of noradamantyldiazirine with the phenanthride precursor of dichlorocarbene or phenylchlorodiazirine in pentane at room temperature produces noradamantylethylenes in 11% yield with slight diastereoselectivity. Cophotolysis of adamantyldiazirine with phenylchlorodiazirine in pentane at room temperature generates adamantylethylenes in 6% yield with no diastereoselectivity. 1H NMR showed the reaction of noradamantyldiazirine + phenylchlorodiazirine to be independent of solvent, and the rate of noradamantyldiazirine consumption correlated with the rate of ethylene formation. Laser flash photolysis showed that reaction of phenylchlorocarbene + adamantene was independent of adamantene concentration. The reaction of phenylchlorocarbene + homoadamantene produces the ethylene products with k = 9.6 × 105 M-1 s-1. Calculations at the UB3LYP/6-31+G(d,p) and UM062X/6-31+G(d,p)//UB3LYP/6-31+G(d,p) levels show the formation of exocyclic ethylenes to proceed (a) on the singlet surface via stepwise addition of phenylchlorocarbene (PhCCl) to bridgehead alkenes adamantene and homoadamantene, respectively, producing an intermediate singlet diradical in each case, or (b) via addition of PhCCl to the diazo analogues of noradamantyl- and adamantyldiazirine. Preliminary direct dynamics calculations on adamantene + PhCCl show a high degree of recrossing (68%), indicative of a flat transition state surface. Overall, 9% of the total trajectories formed noradamantylethylene product, each proceeding via the computed singlet diradical.
Synthesis of Adamantane Derivatives. 49. Substitution Reaction of 1-Adamantyl Chloride with Some Trimethylsilylated Unsaturated Compounds
Sasaki, Tadashi,Usuki, Arimitsu,Ohno, Masatomi
, p. 3559 - 3564 (2007/10/02)
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.
