Formation of (1-adamantylcarbinyl)arenes from 3-azidohomoadamantane-aluminum chloride-aromatic substrates

Margosian, Daniel; Speier, Jon; Kovacic, Peter

doi:10.1021/jo00320a023

Cited by 15 publications

(4 citation statements)

References 3 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Chloride L was obtained from alcohol M and SOCl 2 , while formate N was prepared from M and formic acid, using BF 3 (MeOH) 2 as a catalyst . For the key products, 11-OMe and 11-Cl , 3-homoadamantanol 14 was first converted to 11-Cl with SOCl 2 (reflux, 4 h). , Chloride 11-Cl could then be converted to 11-OMe by refluxing with NaOMe/MeOH for 10 h. Both 11-Cl and 11-OMe were characterized by GC−MS, as well as 1 H and 13 C NMR spectroscopy. The reaction products in Scheme were then verified by GC and GC−MS comparisons with the authentic samples.…”

Section: Resultsmentioning

confidence: 99%

Solvent-Equilibrated Ion Pairs from Carbene Fragmentation Reactions

et al. 2004

View full text Add to dashboard Cite

[R(+) OC Cl(-)] ion pairs were generated in methanol/dichloroethane solutions, with R(+) as the 1-bicyclo[2.2.2]octyl, 1-adamantyl, or 3-homoadamantyl cation. Ion pairs were produced either by the direct fragmentation of alkoxychlorocarbenes (ROCCl), with R = 1-bicyclo[2.2.2]octyl, 1-adamantyl, or 3-homoadamantyl, or by the ring expansion-fragmentation of R'CH(2)OCCl, with R' = 1-norbornyl, 3-noradamantyl, or 1-adamantyl. Correlations of the [ROMe]/[RCl] product ratios as a function of the mole fraction of MeOH in dichloroethane showed that the homoadamantyl chloride ion pairs, produced by either the direct or ring expansion-fragmentations, were identical, solvent- and anion-equilibrated, and precursor independent. Laser flash photolysis experiments gave 20-30 ps as the time required for solvent equilibration and precursor independence. Methanol/chloride selectivities of the (less-stable) 1-adamantyl chloride and 1-bicyclo[2.2.2]octyl chloride ion pairs were not independent of their ROCCl or R'CH(2)OCCl precursors. Computational studies provided transition states for the fragmentations and for the structures of the ion pairs.

show abstract

Section: Resultsmentioning

confidence: 99%

Solvent-Equilibrated Ion Pairs from Carbene Fragmentation Reactions

et al. 2004

View full text Add to dashboard Cite

show abstract

“…Recently, azides of polycyclic bridgehead compounds have attracted an intense interest and research activity due to their high reactivity and some useful properties. For example, secondary azidonorbornenes are potentially important as energetic fuel additives, and azidoadamantanes are used as precursors to various aza-bridged polycyclic systems. , To our knowledge, no direct preparation of azides from bridgehead hydrocarbons was reported in the literature. In particular, 2-azidonorbornane is usually synthesized by addition of HN 3 to norbornene, while azidoadamantanes are prepared from the respective adamantanols or bromoadamantanes …”

Section: Resultsmentioning

confidence: 99%

Preparation, X-ray Crystal Structure, and Chemistry of Stable AzidoiodinanesDerivatives of Benziodoxole

et al. 1996

View full text Add to dashboard Cite

Azidoiodinanes 2 and 4a,b can be prepared from the appropriate benziodoxoles 1 and 3a,b and trimethylsilyl azide in the form of stable, crystalline compounds. A single-crystal X-ray analysis for azide 4b revealed the expected hypervalent iodine distorted T-shaped geometry with the N1−I−O bond angle of 169.5 (2) degrees. The lengths of the bonds to the iodine atom, I−N (2.18 Å), I−O (2.13 Å), and I−C (2.11 Å), are within the range of typical single covalent bonds in organic derivatives of polyvalent iodine, while the previously reported benziodoxoles generally have an elongated I−O bond. The geometry of the I(III)NNN fragment in 4b is similar to the literature electron diffraction data on monomeric iodine azide, IN3, in gas phase. Azidobenziodoxoles 2,4 are potentially useful reagents for direct azidation of organic substrates, such as dimethylanilines, alkanes, and alkenes. Reaction of 2 with dimethylanilines proceeds under mild conditions to afford the respective N-azidomethyl-N-methylanilines in excellent yield. Alkanes, cycloalkanes, and adamantanes react with azidobenziodoxoles 2 or 4b in the presence of radical initiators at 80−132 °C with the formation of tertiary alkylazides, while reaction of norbornane leads to exo-2-azidonorbornane. Under similar conditions cyclohexene is selectively azidated at the allylic position.

show abstract

“…Chemical shifts are reported in p.p.m. (6) relative to SiMe, as internal standard, in CDCl, or (CD3)2S0. Mass spectra were obtained with a JEOL model JMS-D10 mass spectrometer at 75 eV.…”

Section: Resultsmentioning

confidence: 99%

“…This result is different from the reactions of (1) with Reagents: i, PhCSSiMe, (2), AlCI, trimethylsilyl cyanide ' and with arenes,, both of which gave the corresponding 3-substituted 4-azahomoadamantanes. We were therefore interested in the bridgehead substitution route to appropriately functionalized 4-azahomoadamantanes in order to avoid the problems associated with the acid-catalysed ringexpansion route.6 Direct treatment of 3-methoxy-4-azahomoadamantane (5) with a variety of Lewis acids, such as AlCl,, TiCl,, and BF,-OEt2, in benzene gave none of the phenyl substituted product (6) because both extensive complexation of the catalyst by nitrogen and decomposition occurred,…”

mentioning

confidence: 99%

Bridgehead substitution reactions of 3-methoxy-4-azahomoadamantane via N-acyliminium ions. A novel route to some [3,4]-fused 4-azahomoadamantane heterocycles

Sasaki¹,

Eguchi²,

Okano³

et al. 1984

J. Chem. Soc., Perkin Trans. 1

View full text Add to dashboard Cite

Treatment of 3-methoxy-4-methoxycarbonyl-( 9) and 4-acetyl-3-methoxy-4-azahomoadamantane (10) with AICI, in benzene afforded the corresponding 3-phenyl derivatives (1 2) and (1 7) accompanied by considerable amounts of the ring-opened products (13) and (18), respectively. The reaction of compound (9) with phenylethynyltrimethylsilane (2) and AICI, gave the 3-phenylethynyl substitution product (19), while the same reaction of (10) gave the 3-phenylacetyl product (21). The cyclization of compound (1 9) with partially hydrated AICI, afforded the oxazinone (23), the oxazolidinone (24), and the hydrochlorinated product (25); the base-catalysed cyclization of (21 ) gave the 3-pyrrolin-2-one (26). lntramolecular substitution of the 3-methoxy group with the aryl group of the arylureas (28a-c) took place smoothly with AICI, to give the corresponding quinazolinones ( 2 9 a -c ) in good yields.

show abstract

Formation of (1-adamantylcarbinyl)arenes from 3-azidohomoadamantane-aluminum chloride-aromatic substrates

Cited by 15 publications

References 3 publications

Solvent-Equilibrated Ion Pairs from Carbene Fragmentation Reactions

Solvent-Equilibrated Ion Pairs from Carbene Fragmentation Reactions

Preparation, X-ray Crystal Structure, and Chemistry of Stable AzidoiodinanesDerivatives of Benziodoxole

Bridgehead substitution reactions of 3-methoxy-4-azahomoadamantane via N-acyliminium ions. A novel route to some [3,4]-fused 4-azahomoadamantane heterocycles

Contact Info

Product

Resources

About