TY - DATA T1 - High-Yielding, Regiospecific Synthesis of cis(4,4′)-Di(carbomethoxybenzo)-30-crown-10, Its Conversion to a Pyridyl Cryptand and Strong Complexation of 2,2′- and 4,4′-Bipyridinium Derivatives PY - 2008/11/21 AU - Adam M.-P. Pederson AU - Elizabeth M. Ward AU - Daniel V. Schoonover AU - Carla Slebodnick AU - Harry W. Gibson UR - https://acs.figshare.com/articles/dataset/High_Yielding_Regiospecific_Synthesis_of_i_cis_i_4_4_Di_carbomethoxybenzo_30_crown_10_Its_Conversion_to_a_Pyridyl_Cryptand_and_Strong_Complexation_of_2_2_and_4_4_Bipyridinium_Derivatives/2898382 DO - 10.1021/jo801886x.s005 L4 - https://ndownloader.figshare.com/files/4596523 KW - crown ether diol 1 KW - diquat 4 KW - 1 H NMR spectroscopy KW - pyridyl cryptand 12 KW - mass spectrometry KW - Regiospecific Synthesis KW - association constants KW - Pyridyl Cryptand KW - titration calorimetry KW - bipyridinium KW - NOE experiments KW - Ka KW - paraquat KW - cryptand 12 KW - Strong Complexation KW - Cryptand 12 exhibits N2 - A high yielding (93%), regiospecific synthesis of cis(4,4′)-di(carbomethoxybenzo)-30-crown-10 (1c) is reported. The derived crown ether diol 1d was converted to pyridyl cryptand 12 in 44% yield by reaction with pyridine-2,6-dicarbonyl chloride. Binding of two different 4,4′-bipyridinium (paraquat) species (3) and 2,2′-bipyridinium (diquat) 4 by 12 was explored via 1H NMR spectroscopy, NOE experiments, mass spectrometry, X-ray crystallographic analyses, and isothermal titration calorimetry. Cryptand 12 exhibits the highest association constant for diquat ever reported (Ka = 1.9 × 106 M−1) and very high association constants for paraquats (Ka > 105 M−1) in acetone at 22 °C. The binding constant of diquat 4 by cryptand 12 is nearly 6-times higher than any other reported host. ER -