Bicorannulenyl: Stereochemistry of a C40H18 biaryl composed of two chiral bowls

David Eisenberg, Alexander S. Filatov, Edward A. Jackson, Mordecai Rabinovitz, Marina A. Petrukhina, Lawrence T. Scott, Roy Shenhar*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

43 Scopus citations

Abstract

(Figure Presented) The bicorannulenyl molecule is composed of two chiral bowls tethered by a single bond in a helical fashion. This simple combination of two chiral motifs gives rise to rich dynamic stereochemistry, where 12 conformers interconvert through bowl inversions and central bond rotation, and enantiomerizations occur via multistep processes. Interestingly, 8 out of 10 transition states are chiral, giving rise to mostly chiral enantiomerization pathways, where the molecule changes chirality without passing through an achiral conformation. However, analysis of the stereochemical landscape by DFT calculations and variable temperature NMR spectroscopy reveals that the energetically most favorable enantiomerization pathway passes through one of the two achiral transition states. Single-crystal X-ray diffraction corroborates the DFT results and provides information on packing modes of bicorannulenyl molecules in the solid state that have not been seen previously for other buckybowls.

Original languageAmerican English
Pages (from-to)6073-6078
Number of pages6
JournalJournal of Organic Chemistry
Volume73
Issue number16
DOIs
StatePublished - 15 Aug 2008

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