TY - JOUR
T1 - Synthesis, structure, and conformation of aza[1n]metacyclophanes
AU - Vale, Matthew
AU - Pink, Maren
AU - Rajca, Suchada
AU - Rajca, Andrzej
PY - 2008/1/4
Y1 - 2008/1/4
N2 - (Chemical Equation Presented) N-Benzyl substituted aza[1 n]metacyclophanes (n = 4, 6, 8, and 10) were prepared in overall 40% isolated yields via Pd-catalyzed aminations. Analyses of the reaction mixtures showed that aza[14]metacyclophane and the related polymer were the primary products (∼60% overall yield); aza[1n]metacyclophanes up to n = 14 and linear oligomers with up to 20 nitrogen atoms (with at least three types of end groups) were detected. Macrocyclic structures for n = 4, 6, and 10 were confirmed by X-ray crystallography. 1,3-Alternate (D2d) and 1,3,5-alternate (S6) conformations in solution on NMR time scale at low temperatures were found for macrocycles with n = A and n = 6, respectively; the barrier for ring inversion was considerably lower for the larger macrocycle.
AB - (Chemical Equation Presented) N-Benzyl substituted aza[1 n]metacyclophanes (n = 4, 6, 8, and 10) were prepared in overall 40% isolated yields via Pd-catalyzed aminations. Analyses of the reaction mixtures showed that aza[14]metacyclophane and the related polymer were the primary products (∼60% overall yield); aza[1n]metacyclophanes up to n = 14 and linear oligomers with up to 20 nitrogen atoms (with at least three types of end groups) were detected. Macrocyclic structures for n = 4, 6, and 10 were confirmed by X-ray crystallography. 1,3-Alternate (D2d) and 1,3,5-alternate (S6) conformations in solution on NMR time scale at low temperatures were found for macrocycles with n = A and n = 6, respectively; the barrier for ring inversion was considerably lower for the larger macrocycle.
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U2 - 10.1021/jo702151n
DO - 10.1021/jo702151n
M3 - Article
C2 - 18052391
AN - SCOPUS:37549012484
SN - 0022-3263
VL - 73
SP - 27
EP - 35
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
IS - 1
ER -