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A referee suggested that there might be some confusion over how such cyclizations have been described in the past. While the term "cascade" has been widely used to describe the multiple cyclizations that must take place to form the tetra- and pentacyclic systems, it is our understanding that this term implies neither a concerted nor a stepwise mechanism but rather simply a series of cyclizations. The stepwise mechanism in this case implies one or more intermediate carbocations in the pathway being studied. In a concerted reaction the cyclizations might be synchronous, that is, all occurring at the same time, or asynchronous, that is, one cyclization proceeding to some degree before the next one begins to take place. See refs 26 and 27
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A referee suggested that there might be some confusion over how such cyclizations have been described in the past. While the term "cascade" has been widely used to describe the multiple cyclizations that must take place to form the tetra- and pentacyclic systems, it is our understanding that this term implies neither a concerted nor a stepwise mechanism but rather simply a series of cyclizations. The stepwise mechanism in this case implies one or more intermediate carbocations in the pathway being studied. In a concerted reaction the cyclizations might be synchronous, that is, all occurring at the same time, or asynchronous, that is, one cyclization proceeding to some degree before the next one begins to take place. See refs 26 and 27.
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This was also found to be the case for our earlier study of the model system for the ring expansion, ring closure of the C and D rings. See ref 19
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This was also found to be the case for our earlier study of the model system for the ring expansion, ring closure of the C and D rings. See ref 19.
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