Expanded Helicenes: A General Synthetic Strategy and Remarkable Supramolecular and Solid-State Behavior.
J Am Chem Soc
; 139(51): 18456-18459, 2017 12 27.
Article
em En
| MEDLINE
| ID: mdl-29215272
ABSTRACT
A divergent synthetic strategy allowed access to several members of a new class of helicenes, the "expanded helicenes", which are composed of alternating linearly and angularly fused rings. The strategy is based on a three-fold, partially intermolecular [2+2+n] (n = 1 or 2) cycloaddition with substrates containing three diyne units. Investigation of aggregation behavior, both in solution and in the solid state, revealed that one of these compounds forms an unusual homochiral, π-stacked dimer via an equilibrium that is slow on the NMR time scale. The versatility of the method was harnessed to access a selenophene-annulated expanded helicene that, in contrast to its benzannulated analogue, exhibits long-range π-stacking in the solid state. The new helicenes possess low racemization barriers, as demonstrated by dynamic 1H NMR spectroscopy.
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MEDLINE
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2017
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Article