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LiCB(11)Me(12): a catalyst for pericyclic rearrangements
S Moss1, B T King, A de Meijere
1Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309, USA.
Organic Letters
|July 21, 2001
Summary
The lithium salt of the weakly coordinating anion closo-dodecaborate (CB(11)Me(12)(-)) effectively catalyzes various molecular rearrangements, including the transformation of cubane to cuneane. This catalyst demonstrates broad applicability in organic synthesis.
Area of Science:
- Organic Chemistry
- Catalysis
- Carbocation Chemistry
Background:
- Weakly coordinating anions are crucial for stabilizing reactive cationic intermediates.
- The development of efficient catalysts for skeletal rearrangements is a key area in synthetic organic chemistry.
Purpose of the Study:
- To investigate the catalytic activity of the Li(+) salt of CB(11)Me(12)(-) in various molecular rearrangements.
- To explore the scope and efficiency of this catalyst in promoting complex isomerizations.
Main Methods:
- Utilizing the Li(+) salt of CB(11)Me(12)(-) as a catalyst in benzene and 1,2-dichloroethane solutions.
- Monitoring the rearrangement of strained polycyclic hydrocarbons and the Claisen rearrangement of phenyl allyl ether.
Main Results:
- The catalyst successfully promoted the rearrangement of cubane to cuneane, quadricyclane to norbornadiene, basketene to Nenitzescu's hydrocarbon, and diademane to triquinacene.
- A significant acceleration of the Claisen rearrangement of phenyl allyl ether was observed.
Conclusions:
- The Li(+) salt of CB(11)Me(12)(-) is a potent catalyst for a range of molecular rearrangements.
- This catalyst offers a promising new tool for synthetic chemists seeking to access complex molecular architectures.