TY - JOUR
T1 - Internal dynamics and optical rotations predicted for Oh- and O-symmetric cubanes
AU - Hrovat, David A.
AU - Isborn, Christine M.
AU - Kahr, Bart
AU - Borden, Weston Thatcher
PY - 2008
Y1 - 2008
N2 - (Equation Presented) B3LYP/6-31G(d) calculations find that cubanes, persubstituted with NO2 or BF2 groups, are predicted to undergo near-barrierless, internal disrotations. However, as a consequence of the intrinsically higher energies of eclipsed conformations for threefold than for twofold rotors, the threshold mechanisms for octamethyk octakis(trifluoromethyl)-, octakis(trichloromethyl)-, octakis(tribromomethy|)-, octasilylcubane, and octakis(trichlorosilyl)cubane are calculated to be mono- or conrotation. The cubanes with the larger substituents are predicted to be O-symmetric, resolvable, and thus optically active.
AB - (Equation Presented) B3LYP/6-31G(d) calculations find that cubanes, persubstituted with NO2 or BF2 groups, are predicted to undergo near-barrierless, internal disrotations. However, as a consequence of the intrinsically higher energies of eclipsed conformations for threefold than for twofold rotors, the threshold mechanisms for octamethyk octakis(trifluoromethyl)-, octakis(trichloromethyl)-, octakis(tribromomethy|)-, octasilylcubane, and octakis(trichlorosilyl)cubane are calculated to be mono- or conrotation. The cubanes with the larger substituents are predicted to be O-symmetric, resolvable, and thus optically active.
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U2 - 10.1021/ol801762r
DO - 10.1021/ol801762r
M3 - Article
C2 - 18834134
AN - SCOPUS:60949105530
SN - 1523-7060
VL - 10
SP - 4763
EP - 4766
JO - Organic Letters
JF - Organic Letters
IS - 21
ER -