“…Note (Table ) that the deactivating effects of HO and NH 2 as well as F and Cl (HO ≈ NH 2 and F ≈ Cl) run counter to expectations (HO > NH 2 and F > Cl) based on the absence of their potential π – donor resonance effects (depicted by canonical structures 14 and 15 ). It is of interest to note that such interactions are akin to the through‐bond effects considered to dominate the 19 F SCS of 4‐substituted(X) bicyclo[2.2.1]hept‐1‐yl fluorides (n F – σ C−C – σ C−X* ) as well as those responsible for facile fragmentation in the solvolysis of 2 eq , 4 eq – disubstituted adamantanes and exo ‐, exo ‐2,6‐disubstituted norbornanes bearing strong π‐electron donors.…”
+) covering a wide range of electronic substituent effects were calculated using the DFT theoretical model at the B3LYP/6-311 + G(2d,p) and B3LYP/6-31 + G (d) levels of theory, respectively. Linear regression analysis was employed to explore the relationship between the calculated relative hydride affinities (ΔE, kcal/mol) of the appropriate isodesmic reactions for 3/4 and polar field/group electronegativity substituent constants (s F and s x , respectively). The analysis reveals that the ΔE values for both systems are best described by a combination of both substituent constants. The result highlights the importance of the s x dependency of charge delocalization in these systems.
“…Note (Table ) that the deactivating effects of HO and NH 2 as well as F and Cl (HO ≈ NH 2 and F ≈ Cl) run counter to expectations (HO > NH 2 and F > Cl) based on the absence of their potential π – donor resonance effects (depicted by canonical structures 14 and 15 ). It is of interest to note that such interactions are akin to the through‐bond effects considered to dominate the 19 F SCS of 4‐substituted(X) bicyclo[2.2.1]hept‐1‐yl fluorides (n F – σ C−C – σ C−X* ) as well as those responsible for facile fragmentation in the solvolysis of 2 eq , 4 eq – disubstituted adamantanes and exo ‐, exo ‐2,6‐disubstituted norbornanes bearing strong π‐electron donors.…”
+) covering a wide range of electronic substituent effects were calculated using the DFT theoretical model at the B3LYP/6-311 + G(2d,p) and B3LYP/6-31 + G (d) levels of theory, respectively. Linear regression analysis was employed to explore the relationship between the calculated relative hydride affinities (ΔE, kcal/mol) of the appropriate isodesmic reactions for 3/4 and polar field/group electronegativity substituent constants (s F and s x , respectively). The analysis reveals that the ΔE values for both systems are best described by a combination of both substituent constants. The result highlights the importance of the s x dependency of charge delocalization in these systems.
The acidolysis of 3-endo-azidomethylbicyclo[3.3.1 lnon-6-ene (3) with methanesulphonic acid gave 4-azahomoadamant-4-ene (5) which was also produced from 3-endohydroxymethylbicyclo[3.3.1] non-6-ene (6) on treatment with NaN,-MeS0,H.The formation of (5) was rationalized by a x route cyclization followed by acidolytic ring expansion of intermediate azides on the basis of acidolysis of dideuterioderivatives. The above route was extended to synthesis of 2,2-(1 6) and 7,7-dimethyl-4-azahomoadamant-4-enes (1 7). The acidolysis of 3-endo-azidobicyclo[3.3.1] non-6-ene ( 2 3 ) gave 2-aza-adamantan-anti-4-01 (26) via a x-N+ type cyclization.Organic azides are well-known as excellent synthetic starting materials for various nitrogen-containing organic molecules, although, studies utilizing azide functionalization of carbocycles, particularly, bi-and tri-cycles seem, as yet, to be underdeveloped.2 We have therefore been pursuing attractive synthetic routes to aza-adamantane and related derivatives by utilizing azide functionalization of bi-and tri-carbocycles in order to study their biological proper tie^.^ Previously, we reported convenient and efficient synthesis of 4-azahomoadamant-4-ene and its 5-substituted derivatives by acidolysis and/or photolysis of 2-a~idoadamantanes.~ Here, we report the synthesis of 3-endo-azidomethyl-and -azidobicyclo[3.3.1]non-6-enes and their acidolysis behaviour, the latter providing novel routes to 4-azahomoadamant-4-enes and 4-hydroxy-2aza-adamant ane, respectively .* Eu(fod)3 = tris-(
Die Umsetzung bromierter Adamantanverbindungen mit (Trimethylstanny1)lithium lieferte eine Reihe von (Trimethylstanny1)adamantan-Derivaten. Wir fanden zusatzlich Fragmentierungs-und Reduktionsprodukte, die Ruckschlusse auf den Mechanismus zulienen. iiberraschend ist die hohe Stereoselektivitat der meisten Reaktionen. Durch Wurtz-Synthese wurde auch 2-Adamantyltriphenylstannan erhalten.
Synthesis of (Trimethylstannyl)adamantane DerivativesReaction of brominated adamantane compounds with (trimethylstanny1)lithium afforded a series of (trimethylstanny1)adamantane derivatives. Additionally, we found products from fragmentation and reduction reactions which allowed conclusions concerning the mechanisms. Surprisingly high stereoselectivities were observed in most instances. By Wurtz synthesis we obtained 2-adamantyltriphen ylstannane.Neben siliciumhaltigen" Adamantanderivaten interessierten uns fur unsere '3C-NMR-spektroskopischen Untersuchungen auch solche mit anderen elektropositiven Substituenten ohne freie Elektronenpaare. Aus diesem Grunde synthetisierten wir eine Anzahl substituierter 2-Adamantyltrimethylstannane.
Die Umsetzung der Alkalimetallderivate von Organometallanionen ist seit uber 50Jahren erfolgreich fur die Synthese von Tetraalkylzinn-Verbindungen verwendet worden2-". In neuerer Zeit sind eine Reihe von Arbeiten erschienen, die sich mit dem Mechanismus und der Stereochemie dieser Reaktion beschaftigen (vgl. Lit. 6-14) und darin zitierte Arbeiten).Zur Synthese unserer Zielverbindungen bedienten wir uns daher dieser Reaktion, wobei bromhaltige Ausgangsverbindungen mit (Trimethy1stannyl)lithium (Me3SnLi) in Tetrahydrofuran (THF) umgesetzt wurden. So stellten wir z. B. den einfachsten Vertreter 2-Adamantyltrimethylstannan (2) dar, der bereits literaturbekannt ist 1 3 9 1 5 * 1 6 ) : 1 2
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