Abstract
The alicyclic diol 2 is known to adopt five different types of crystallattice: the pure solid, cocrystalline compounds with water or certainphenols, and two different types of lattice inclusion system (helicaltubulates and ellipsoidal clathrates). Self-resolution only occurs onforming the helical tubulate inclusion compounds. Its close analogue2,7-bis(trifluoromethyl)tricyclo[4.3.1.13,8]un-decane-syn-2,syn-7-diol 4 was synthesised to examine the influence ofreplacing CH3- by CF3-groups. It no longer formslattice inclusion compounds but does form a cocrystalline solid withdimethyl sulfoxide (DMSO). Crystal structures of 4[C13H16O2F6,P21/c, a 7.8636(6), b 13.1020(7), c 25.319(2) Å, β101.526(4)°, Z 8, R 0.044] and (4)V_2.VD/MSO[(C13H16O2F6)2⋅C2H6SO,P212121, a 7.249(1), b 16.064(3),c 25.347(4) Å, Z 4, R 0.033] were determined. In solid diol 4 themolecules are linked through (–-O–-H)4 rings toproduce layers of chirally pure enantiomers but the net crystal structure,which comprises layers of alternating handedness, is achiral. In contrast,complexation of 4 with DMSO by means of two -–O-–H.O=Shydrogen bonds induces complete enantiomeric self-resolution.
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Bishop, R., Downing, G.a., Craig, D.C. et al. Enantiomeric Self-Resolution through Dimethylsulfoxide Complexation. Journal of Inclusion Phenomena 31, 145–160 (1998). https://doi.org/10.1023/A:1007958031910
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DOI: https://doi.org/10.1023/A:1007958031910