TY - JOUR
T1 - Synthesis of fluoranthenes and indenocorannulenes
T2 - Elucidation of chiral stereoisomers on the basis of static molecular bowls
AU - Wu, Yao Ting
AU - Hayama, Tomoharu
AU - Baldridge, Kim K.
AU - Linden, Anthony
AU - Siegel, Jay S.
PY - 2006/5/31
Y1 - 2006/5/31
N2 - Cycloaromatization of a peri diyne with an external alkyne provides a general route to indenofused polynuclear aromatics. Fluoranthenes 9 (or 13) are easily accessible in good to excellent yields (75-99%; 18 examples) from the reaction of symmetric (or asymmetric) diynes 4 and alkynes 5 (or norbornadiene) in the presence of Wilkinson's catalyst. This formal [(2+2)+2] cycloaddition can also be applied to generate various indenocorannulenes 28 from 2,3-diethynylcorannulene derivatives 27 and alkynes 5. The indenocorannulenes 28 exist in a static bowl form at room temperature with bowl-to-bowl inversion barriers higher than 24 kcal/mol. This barrier renders the rate of inversion slow enough at room temperature to establish a class of chiral, bowl-shaped stereoiomers containing no tetrahedrally ligated atoms. The crystal structure of 28g provides insight into the bowl-shaped geometry of these compounds. This new synthetic method occurs under neutral conditions and tolerates various functional groups (e.g., alkyl, aryl, alcohols, and esters).
AB - Cycloaromatization of a peri diyne with an external alkyne provides a general route to indenofused polynuclear aromatics. Fluoranthenes 9 (or 13) are easily accessible in good to excellent yields (75-99%; 18 examples) from the reaction of symmetric (or asymmetric) diynes 4 and alkynes 5 (or norbornadiene) in the presence of Wilkinson's catalyst. This formal [(2+2)+2] cycloaddition can also be applied to generate various indenocorannulenes 28 from 2,3-diethynylcorannulene derivatives 27 and alkynes 5. The indenocorannulenes 28 exist in a static bowl form at room temperature with bowl-to-bowl inversion barriers higher than 24 kcal/mol. This barrier renders the rate of inversion slow enough at room temperature to establish a class of chiral, bowl-shaped stereoiomers containing no tetrahedrally ligated atoms. The crystal structure of 28g provides insight into the bowl-shaped geometry of these compounds. This new synthetic method occurs under neutral conditions and tolerates various functional groups (e.g., alkyl, aryl, alcohols, and esters).
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U2 - 10.1021/ja058391a
DO - 10.1021/ja058391a
M3 - Article
C2 - 16719467
AN - SCOPUS:33744782312
VL - 128
SP - 6870
EP - 6884
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 21
ER -