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Synthesis, Structure, and Conformation of Aza[1_n]metacyclophanes

Supporting Info

Matthew Vale,^† Maren Pink,^‡ Suchada Rajca,^† and Andrzej Rajca*^†

Department of Chemistry, University of Nebraska, Lincoln, Nebraska 68588-0304, and IUMSC, Department of Chemistry, Indiana University, Bloomington, Indiana 47405-7102

J. Org. Chem., 2008, 73 (1), pp 27–35

DOI: 10.1021/jo702151n

Publication Date (Web): December 6, 2007

†

University of Nebraska.

‡

Indiana University.

Corresponding author. Fax: (402) 472-9402.

, arajca1@unl.edu

Abstract

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[1_n]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 (D₂_d) and 1,3,5-alternate (S₆) conformations in solution on NMR time scale at low temperatures were found for macrocycles with n = 4 and n = 6, respectively; the barrier for ring inversion was considerably lower for the larger macrocycle.

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Published In Issue January 04, 2008
Received October 3, 2007

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